CN1603131A - Recording medium - Google Patents

Abstract

This recording medium with a recording layer provided on a substrate is characterized in that the recording layer contains a polymer which has a thioether bond, whose sulfur equivalent is 1.2 meq/g or more, and wherein an inorganic/organic ratio (I/O value) shown in the organic conceptual diagram is 0.5 or more. To provide a recording medium which enables the formation of a high-resolution and high-density image, and which exerts the excellent effect of preventing fading from being caused by an ozone gas in the atmosphere, without causing bleeding with time, even if stored for a long period of time under the high-temperature and high-humidity environment after printing.

Description

Recording medium

Technical field

The present invention relates to can be used for the recording medium in ink jet recording method, thermal photography method, pressure sensitive recording method, photosensitive record method, the transfer printing type recording method etc., particularly relate to the recording medium that is supplied in the ink jet recording method, relate to specifically that printing ink is accepted performance, glossiness, light resistance is good and image section through the time ooze profit and few recording medium that fades.

Background technology

In recent years,, developed various information processing systems, also developed the recording method and the tape deck that are fit to this information processing system, and respectively controlled oneself and be practical along with developing rapidly of IT industry.

As the recording method that has been practical, except the silver halide photography method, can enumerate xerography, ink jet recording method, thermal photography method, pressure sensitive recording method, thermal transfer etc.And in above-mentioned any recording method, require to obtain clear picture, painted high resolution image too.

In these recording methods, ink jet recording method has can be recorded in the multiple advantages such as the relatively more cheap and miniaturization of material, hardware (device), noise are few that are recorded, and therefore can also be widely used in so-called domestic consumer except office.

In addition,, also can obtain the high image quality record thing of so-called similar photo,, also develop the record-paper that various ink mist recordings are used along with the progress of this hardware (device) along with the high-resolutionization of ink-jet printer in recent years.

As the desired characteristic of the recording medium that this ink mist recording is used, generally can enumerate (1) has rapid-drying properties (infiltration rate of printing ink is fast); (2) (the diameter of printing ink point suitable and even (not oozing profit); (3) graininess is good; (4) just round property height; (5) color density height; (6) excitation height (not obfuscation); (7) resistance to water of sensitization part and light resistance, ozone resistance are good; (8) the whiteness height of record-paper; (9) the having good keeping qualities of record-paper (even long preservation can not cause that xanthochromia is painted yet, after the long preservation image can not ooze profit (through the time to ooze profit good); (10) not yielding, dimensional stability good (it is very little to crispatura); (11) the hardware maneuverability is good etc.

Moreover, in the purposes of the photograph glossy paper that uses for the high image quality record thing that obtains so-called similar photograph, except above-mentioned various characteristics, also require the feel etc. of the sensitive paper shape of glossiness, the surface smoothing of glossiness, sensitization part, similar silver halide photography.

In order to improve above-mentioned various characteristics, developed the ink jet recording medium that in ink-receiver layer, has porous structure in recent years and made it practicability.Because such ink jet recording medium has porous structure, so printing ink acceptance (rapid-drying properties) is good and have a high gloss.

The ink-receiver layer that for example proposed to contain fine inorganic pigment particles and water-soluble resin, has a high voidage is set at the ink jet recording medium (for example, with reference to patent documentation 1 and 2) on the supporter.

These paper used for recording, the ink jet recording medium of the ink-receiver layer that is made of the porous structure that uses silica inorganic pigment microparticles particularly is set and since its structure can make ink absorption good, have the high printing ink that can form high-definition picture and accept performance and can show high glaze.

Yet because these materials are porous matter overlay film, the permeability of oxygen is big, thus the deterioration of the composition that contains in the promotion ink-receiver layer.Moreover, along with the water adsorption on the silica surface, passing that can be in time produce image ooze profit (hereinafter referred to as " and through the time ooze profit ").

In addition, airborne minimum gas is ozone particularly, become document image in time passing and the reason of fading.In the above-mentioned recording materials that constitute by ink-receiver layer, owing to contain more space, therefore be subjected to the influence of airborne ozone easily and cause document image to fade with porous structure.Therefore, for above-mentioned recording materials, be very important characteristic for the patience (ozone resistance) of ozone in the air with ink-receiver layer of porous structure.

In order to improve various characteristics such as preventing sheding tintability, reported multiple structure of in ink-receiver layer, adding sulfur-containing compound.

For example proposed to contain the ink jet recording medium of thio-ether type compounds.(for example with reference to patent documentation 3 and 4.)

Yet the exemplary compounds of record all is hydrophobic low molecular compounds in the patent documentation 3 and 4, is water-insoluble.Therefore be difficult to be incorporated in the coating liquid,, also can reduce the glossiness of ink jet recording medium even add with the form of emulsion.

In addition, proposed to use the method (for example with reference to patent documentation 5 and 6) of the thio-ether type compounds that contains hydrophilic radical.

Yet, though the exemplary compounds of record can be confirmed the effect of ozone resistance in patent documentation 5 and 6 owing to be hydrophilic low molecular compound, so can cause under the hot and humid condition through the time ooze lubricant nature deterioration.Moreover such compound majority is a low-melting compound, if under low temperature environment for example under the environment below 5 ℃ through 1 time-of-week, the problem that so-called thio-ether type compounds is separated out on the record-paper surface then also appears.

Moreover, the example of use polysulfide (disulphide and trisulfide, the equal less than 1000 of any molecular weight) is also arranged, but the improvement effect of the ozone resistance of these compounds is insufficient (for example with reference to patent documentation 7.)。

On the other hand, proposed to contain the macromolecular compound of thioether bond (for example with reference to patent documentation 8 and 9.)。

Yet, in the patent documentation 8 and 9 in the exemplary compounds (the maybe compound that can analogize) of record because sulfur content low (1meq/g following), so the improvement effect of ozone resistance is insufficient.

In addition, proposed to use the synthetic cationic addition polymers of specific thioether (for example with reference to patent documentation 10 and 11.)。

Yet though can improve resistance to water when containing this cationic addition polymers in ink-receiver layer, the ozone resistance of this moment is insufficient.

Moreover, specific macromolecular compound (for example with reference to patent documentation 12) has been proposed.

Yet, in the patent documentation 12 macromolecular compound of record be Tg at the organic filler more than 70 ℃, so glossiness is insufficient.

[patent documentation 1] spy opens flat 10-119423 communique

[patent documentation 2] spy opens flat 10-217601 communique

[patent documentation 3] spy opens clear 64-36479 communique

[patent documentation 4] spy opens flat 1-115677 communique

[patent documentation 5] spy opens the 2002-86904 communique

[patent documentation 6] spy opens the 2002-36717 communique

[patent documentation 7] spy opens the 2001-315432 communique

[patent documentation 8] spy opens flat 11-58941 communique

[patent documentation 9] spy opens clear 63-260477 communique

[patent documentation 10] spy opens flat 11-268406 communique

[patent documentation 11] spy opens the 2001-270227 communique

[patent documentation 12] spy opens the 2003-54118 communique

Summary of the invention

Problem of the present invention is to solve above-mentioned existing problems, reaches following purpose.Promptly, the object of the present invention is to provide and to form high-resolution, high-density images, even after the sensitization can not produce under the long-time situation of preserving under the environment of hot and humid degree yet through the time ooze profit, and prevent because the good recording medium of fading effect that ozone gas causes in the atmosphere.

In view of this present situation, the present inventor is through attentively discovering, the recording medium that contains particular polymers as follows in the recording layer of supporter can solve above-mentioned problem, thereby has finished the present invention.

That is, the invention provides as follows:

＜1〉a kind of recording medium, it is the recording medium that on supporter, has recording layer, it is characterized in that, contain in the above-mentioned recording layer have thioether bond, the sulphur equivalent in inorganic nature/organic property of representing more than the 1.2meq/g and by organic conceptional diagram than (I/O) value at the polymer more than 0.5.

＜2〉recording medium of record＜1〉is characterized in that above-mentioned polymer is for containing the polymer of the part-structure shown in the following general formula (1).

General formula (1)

P-Y-S-

[in the general formula (1), P represents to contain the polymer residue or the oligomer residue of repetitive.Y represents the linking group of singly-bound or divalent].

＜3〉＜1〉or＜2 in the recording medium of record, it is characterized in that above-mentioned polymer is for containing the polymer of the part-structure shown in the following general formula (2).

General formula (2)

[in the general formula (2), R ¹Expression hydrogen atom or methyl.R ²Expression alkyl or aryl, J represents the linking group of singly-bound or divalent].

＜4〉＜1 〉～＜3〉recording medium of putting down in writing in any one is characterized in that above-mentioned polymer is for containing the polymer of the part-structure shown in the following general formula (3).

General formula (3)

[in the general formula (3), R ¹¹And R ¹²Represent hydrogen atom or methyl independently of one another.R ¹³Expression alkyl or aryl.R ¹⁴, R ¹⁵And R ¹⁶Represent hydrogen atom or alkyl independently of one another.Y ¹Represent the linking group of divalent independently of one another with Z.m ¹And n ¹The mole % of repetitive in the expression polymer, 10≤m ¹≤ 95,5≤n ¹≤ 90.X ^-Be expressed as balance anion].

＜5〉＜1 〉～＜4〉recording medium of putting down in writing in any one is characterized in that above-mentioned polymer is for containing the polymer of the part-structure shown in the following general formula (4).

General formula (4)

[in the general formula (4), R ²⁰Expression hydrogen atom or methyl.R ²¹Expression alkyl or aryl.W represents the linking group of divalent.A represents to contain the unit of ethene unsaturated double-bond group.m ²And n ²The mole % of repetitive in the expression polymer, 50≤m ²≤ 95,5≤n ²≤ 50].

＜6〉＜1 〉～＜5〉recording medium of putting down in writing in any one, the sulphur equivalent that it is characterized in that above-mentioned polymer is more than 3meq/g.

＜7〉＜1 〉～＜6〉recording medium of putting down in writing in any one is characterized in that above-mentioned polymer is to have polymer water-soluble or the self-emulsifying characteristic.

＜8〉＜1 〉～＜7〉recording medium of putting down in writing in any one is characterized in that above-mentioned polymer is by polybutadiene base polymer or polyisoprene base polymer derived polymers.

＜9〉＜1 〉～＜8〉recording medium of putting down in writing in any one is characterized in that above-mentioned recording layer is an ink-receiver layer, is ink jet recording medium.

＜10〉recording medium of record is characterized in that also containing in the above-mentioned ink-receiver layer water-soluble resin＜9 〉.

＜11〉＜9〉or＜10 in the record recording medium, it is characterized in that also containing in the above-mentioned ink-receiver layer particulate.

＜12〉＜9 〉～＜11〉recording medium of putting down in writing in any one, it is characterized in that containing in the above-mentioned ink-receiver layer can the cross-linked, water-soluble resin crosslinking agent.

＜13〉＜9 〉～＜12〉recording medium of putting down in writing in any one is characterized in that also containing in the above-mentioned ink-receiver layer mordant.

＜14〉＜9 〉～＜13〉recording medium of putting down in writing in any one, it is characterized in that above-mentioned ink-receiver layer is to make to apply to contain above-mentioned polymer, the layer that the coat crosslinking curing of the coating liquid of particulate and water-soluble resin forms, above-mentioned crosslinking curing can by to above-mentioned coating liquid or/and add crosslinking agent in the following alkaline solution, and (1) apply above-mentioned coating liquid and when forming coat or (2) apply in the dry way of the formed coat of above-mentioned coating liquid and this coat show falling rate of drying before whenever, pH is surpassed 7 alkaline solution is supplied in the above-mentioned coat and obtains.

By the present invention, though can provide have the good ink absorbability, image color is good, the light resistance of image section, resistance to water, anti-gaseousness is good and can not produce under the long-time situation of preserving under the environment of hot and humid degree yet through the time ooze the recording medium of profit.

The specific embodiment

Recording medium of the present invention is characterised in that, in the recording layer of supporter, contain have thioether bond, the sulphur equivalent in inorganic nature/organic property of representing more than the 1.2meq/g and by organic conceptional diagram than (I/O) value at the polymer more than 0.5, particularly preferably be the ink jet recording medium that above-mentioned recording layer is an ink-receiver layer.

Moreover, also can contain particulate, water-soluble resin etc. according to needs in the above-mentioned ink jet recording medium root.Below describe at ink jet recording medium.

＜ink-receiver layer (recording layer) 〉

(polymer)

The polymer that uses in the ink-receiver layer of above-mentioned ink jet recording medium (recording layer), as already described, for have thioether bond, sulphur equivalent more than the 1.2meq/g and the inorganic nature of representing by organic conceptional diagram/organic property than (I/O) value the polymer more than 0.5 (below be sometimes referred to as " polymer of the present invention ".)。

Here, so-called sulphur equivalent is meant the equivalent (mmol) of the sulphur atom that contains in every 1g polymer, is the value of representing with meq/g.When the compound of molecular weight 1000 contains the 1mol sulphur atom, be 1meq/g for example.

The sulphur equivalent of the polymer of the invention described above is more than 1.2meq/g, particularly preferably in more than 3meq/.If not enough 1.2meq/g, then the effect of ozone resistance becomes insufficient.

In addition, the so-called above-mentioned inorganic nature of being represented by organic conceptional diagram/organic property is than (I/O value), be meant the parameter of expression compound or substituent hydrophily/lipophile yardstick, in " organic conceptional diagram " (first Tian Shansheng work three was published 1984 altogether), it had detailed explanation.I represents inorganic nature, and O represents organic property, and the I/O value is big more then represents inorganic nature big more (polarity height, hydrophily big).The I/O value of polymer of the present invention must be more than 0.5, preferably more than 0.7, below 3.0, more preferably more than 0.8, below 2.5.If I/O value less than 0.5, then the glossiness of video picture laminar surface reduces, and handles suitability and reduce.

Above-mentioned I/O value is for to place on one of method to the functional group of each functional group's setup parameter, and all there are inorganic value, organic value in each functional group.The functional group that polymer of the present invention need be constituted according to the decision of this parameter.Compound as forming this polymer can use known compound.

As polymer of the present invention, be preferably the polymer of the part-structure that contains following general formula (1) expression.

General formula (1)

P-Y-S-

In the general formula (1), P represents to contain the polymer residue or the oligomer residue of repetitive.Y represents the linking group of singly-bound or divalent.

As above-mentioned polymer residue or oligomer residue, what can preferably enumerate is (methyl) acrylate copolymer, (methyl) acrylate polymer, (methyl) acrylamide polymer, (methyl) N substituted acrylamide polymer, aromatic vinyl polymer, vinyl ester polymer, vinyl halides based polyalcohol, vinyl cyanide based polyalcohol, diolefin compound polymer.

On the other hand; as the linking group of above-mentioned divalent, what can preferably enumerate is ehter bond, ester bond, thioester bond, carbonic acid ester bond, carbamoyl, alkylidene (for example methylene, ethylidene, propylidene, trimethylene, tetramethylene, hexa-methylene, eight methylene), arlydene (for example phenylene) or the group that obtained by these combinations.

Also have, " (methyl) acrylic " is meant " acrylic " or " methylpropenyl " in this manual.

In addition, as polymer of the present invention, be preferably the polymer of the part-structure that contains following general formula (2) expression.

General formula (2)

In the general formula (2), R ¹Expression hydrogen atom or methyl.J represents the linking group of singly-bound or divalent, as the divalent linking group of representing with this J, what can enumerate is alkylidene (for example methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene, cyclohexylidene, 2-hydroxy propylidene etc.), arlydene (for example phenylene), ehter bond, ester bond, thioether bond, thioester bond, carbonic acid ester bond, amide groups and by a plurality of linking groups that constitute of these groups.

In addition, R ²Expression alkyl or aryl.As above-mentioned R ²The alkyl of expression, preferably carbon number is 1～18 alkyl, more preferably carbon number is 1～12 alkyl.Specifically can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, decyl and dodecyl, these alkyl can also contain substituting group (for example hydroxyl, carboxyl, sulfo group, alkoxy carbonyl group, carbamoyl, sulfamoyl, cyano group, amino, alkoxyl, phenyl etc.) and ester bond, ehter bond and amido link.

As above-mentioned R ²The aryl of expression, preferred carbon number are 6～12 aryl.Specifically can enumerate phenyl and naphthyl, these aryl can also contain substituting group.

As above-mentioned R ¹³Preferred carbon number is the group that also contains substituting group (for example hydroxyl, carboxyl, sulfo group) on 1～12 unsubstituted alkyl and this alkyl, specifically preferable methyl, ethyl, ethoxy, 2,3-dihydroxypropyl, 2-carboxy ethyl, 3-carboxyl propyl group and 3-sulphoxylic acid base (sulfoxy) propyl group.

In addition, preferably also contain hydrophilic radical in the polymer of the present invention.As hydrophilic radical, can enumerate hydroxyl, carboxyl, sulfo group, carbamoyl, sulfamoyl, amino, ammonio base, amidino groups etc., preferred especially hydroxyl, ammonio base, amino, carbamoyl.

Moreover, as polymer of the present invention, also preferably contain the polymer of the part-structure of following general formula (3) expression.

General formula (3)

In the above-mentioned general formula (3), R ¹¹And R ¹²Represent hydrogen atom or methyl independently of one another.R ¹³Expression alkyl or aryl.R ¹⁴, R ¹⁵And R ¹⁶Represent hydrogen atom or alkyl independently of one another.Y ¹Represent the linking group of divalent independently of one another with Z.m ¹And n ¹The mole % of repetitive in the expression polymer, 10≤m ¹≤ 95,5≤n ¹≤ 90.X ^-Be expressed as balance anion.

R in the above-mentioned general formula (3) ¹³Expression alkyl or aryl.

As above-mentioned R ¹³The alkyl of expression, preferred carbon number is 1～18 alkyl, more preferably carbon number is 1～12 alkyl.Specifically can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, decyl and dodecyl, these alkyl can also contain substituting group (for example hydroxyl, carboxyl, sulfo group, alkoxy carbonyl group, carbamoyl, sulfamoyl, cyano group, amino, alkoxyl, phenyl etc.) and ester bond, ehter bond and amido link.

As above-mentioned R ¹³The aryl of expression, preferred carbon number are 6～12 aryl.Specifically can enumerate phenyl and naphthyl, these aryl can also contain substituting group.

As above-mentioned R ¹³Preferred carbon number is the group that also contains substituting group (for example hydroxyl, carboxyl, sulfo group) on 1～12 unsubstituted alkyl and this alkyl, specifically preferable methyl, ethyl, ethoxy, 2,3-dihydroxypropyl, 2-carboxy ethyl, 3-carboxyl propyl group and 3-sulphoxylic acid base (sulfoxy) propyl group.

As above-mentioned R ¹⁴, R ¹⁵Or R ¹⁶The alkyl of expression can be enumerated and above-mentioned R ¹³The same group of alkyl of expression.

As above-mentioned R ¹⁴, R ¹⁵Or R ¹⁶, be preferably hydrogen atom, methyl and ethyl.

In the above-mentioned general formula (3), X ^-Be expressed as balance anion.As above-mentioned X ^-The one-tenth balance anion of expression can be enumerated halide ion (Cl ^-, Br ^-, I ^-), azochlorosulfonate acid ion, alkyl sulfonic acid ion, aryl sulfonic acid ion, alkyl carboxylic acid ion and aryl carboxylic acid ion etc.

In the above-mentioned general formula (3), Y ¹Represent the linking group of divalent independently of one another with Z.As above-mentioned Y ¹Or the divalent linking group represented of Z, what can enumerate is alkylidene (for example methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene, cyclohexylidene, 2-hydroxy propylidene etc.), arlydene (for example phenylene), (sulphur) ehter bond, (sulphur) ester bond and amido link and by a plurality of linking groups that combine in these groups.

In the above-mentioned general formula (3), m ¹And n ¹The mole % of repetitive in the expression polymer, 10≤m ¹≤ 95,5≤n ¹≤ 90.As above-mentioned m ¹And n ¹, 50≤m preferably ¹≤ 95,5≤n ¹≤ 50.m ¹And n ¹If at 10≤m ¹≤ 95,5≤n ¹In≤90 the scope, then prevent because the effect of fading that ozone gas causes in the atmosphere becomes more remarkable.

Moreover, as polymer of the present invention, also be preferably the polymer of the part-structure that contains following general formula (4) expression.

General formula (4)

In the general formula (4), R ²⁰Expression hydrogen atom or methyl.R ²¹Expression alkyl or aryl.W represents the linking group of divalent.A represents to contain the unit of ethene unsaturated double-bond group.m ²And n ²The mole % of repetitive in the expression polymer, 50≤m ²≤ 95,5≤n ²≤ 50.

R in the above-mentioned general formula (4) ²¹Expression alkyl or aryl.

As above-mentioned R ²¹The alkyl of expression, preferred carbon number is 1～18 alkyl, more preferably carbon number is 1～12 alkyl.Specifically can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, decyl and dodecyl, these alkyl can also contain substituting group (for example hydroxyl, carboxyl, sulfo group, alkoxy carbonyl group, carbamoyl, sulfamoyl, cyano group, amino, alkoxyl, phenyl etc.) and ester bond, ehter bond and amido link.

As above-mentioned R ²¹The aryl of expression, preferred carbon number are 6～12 aryl.Specifically can enumerate phenyl and naphthyl, these aryl can also contain substituting group.

As above-mentioned R ²¹, the preferred alkyl that is replaced by hydrophilic radical is the alkyl that 1～8 hydrophilic radical replaces by carbon number more preferably.Specifically preferred specifiable is ethoxy, 2,3-dihydroxypropyl, 2-carboxy ethyl, 3-carboxyl propyl group, 3-sulphoxylic acid base (sulfoxy) propyl group, 2-amino-ethyl, N, N-diamino ethyl and triethyl ammonium ethyl.

In the above-mentioned general formula (4), W represents the linking group of divalent.As the divalent linking group that above-mentioned W represents, what can enumerate is alkylidene (for example methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene, cyclohexylidene, 2-hydroxy propylidene etc.), arlydene (for example phenylene), (sulphur) ehter bond, (sulphur) ester bond and amido link and by a plurality of linking groups that combine in these.

In the above-mentioned general formula (4), A represents to contain the unit of ethene unsaturated double-bond group.As these unit, specifiable is allyl acrylate, allyl methacrylate, 1,2-butadiene, 1, and 4-butadiene, isoprene etc., preferred 1,2-butadiene, 1,4-butadiene, isoprene.

In the above-mentioned general formula (4), m ²And n ²The mole % of repetitive in the expression polymer, 50≤m ²≤ 95,5≤n ²≤ 50.As above-mentioned m ²And n ², 70≤m preferably ²≤ 95,5≤n ²≤ 30.Above-mentioned m ²And n ²If at 50≤m ²≤ 95,5≤n ²In≤50 the scope, then prevent because the effect of fading that ozone gas causes in the atmosphere will become more remarkable.

Polymer of the present invention is preferably water-soluble or has self emulsifiable polymer.In the present invention, above-mentioned water-soluble polymer is illustrated under 25 ℃ of the room temperatures has deliquescent polymer substance more than the 0.1 quality % to glassware for drinking water, and this dissolubility is preferably more than 0.5 quality %, especially more preferably more than 1 quality %.

In addition, above-mentioned self-emulsifying polymer is illustrated in the polymer substance that has the stable emulsion dispersiveness with respect to the water system decentralized medium with the above concentration of 0.5 quality % under 25 ℃ of the room temperatures, and this concentration is preferably more than 1 quality %, especially more preferably more than 3 quality %.

The weight average molecular weight of polymer of the present invention is preferably 1000～1000000, and more preferably 2000～100000.

If above-mentioned weight average molecular weight is 1000～1000000, then can further improve resistance to water and through the time ooze the improved effect of profit, also further improve simultaneously and handle suitability.

Synthetic method as polymer of the present invention, can enumerate by polycondensation, addition polymerization and (pay and add coincidence, addition polymerization, belong to chain reaction), addition polymerization (heavily pays and adds, polyaddition, majority belongs to step-reaction), addition condensation, ring-opening polymerisation or utilize synthetic method of high molecular weight reactive etc.Wherein, polymer of the present invention is preferably the polymer that obtains by addition reaction, preferred specifiable be the polymer that for example obtains by addition polymerization (for example containing the radical polymerization of the vinyl monomer of thioether bond) and high molecular weight reactive (for example the nucleophilic addition and the free radical addition of the polymer side chain that contains reactive group being reacted) with the polymerization of sulfhydryl compound as the vinyl monomer of chain-transferring agent.

In addition, polymer of the present invention is preferably especially by polybutadiene base polymer or polyisoprene base polymer derived polymers.Obtain the method for the polymer of the invention described above as being derived by polybutadiene base polymer or polyisoprene base polymer, specifiable is polybutadiene base polymer or polyisoprene base polymer and the method for sulfhydryl compound generation free radical addition more than a kind or 2 kinds of making.In addition, under the situation of polymer of the present invention for the polymer of the part-structure that contains above-mentioned general formula (3) expression, specifiable is to make polybutadiene base polymer or polyisoprene base polymer and the method that contains the sulfhydryl compound of cationic group and the sulfhydryl compound generation free radical addition more than a kind in addition.

As above-mentioned sulfhydryl compound, for example as the above-mentioned sulfhydryl compound that contains the cationic group, specifiable is 2-aminoothyl mercaptan hydrochloride, 2-aminoothyl mercaptan-p-methyl benzenesulfonic acid, N, N-dimethylaminoethyl mercaptides hydrochlorate, N, N-diethylamino ethanethiol hydrochloride, chlorination 2-mercaptoethyl trimethyl ammonium, N, N-dimethylamino ethyl mercaptan mesylate, N, N-dimethylamino ethyl mercaptan acetate etc., as above-mentioned sulfhydryl compound in addition, specifiable is 2 mercapto ethanol, the 3-mercaprol, α-thioglycerol, TGA, the 3-mercaptopropionic acid, 2 mercaptopropionic acid, the 3-mercaptopropionic acid ethyl ester, the own ester of 3-mercaptopropionic acid, 3-mercaptopropionic acid monooctyl ester, ethyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, benzyl mercaptan, the 4-mercapto-phenol, 4-sulfydryl toluene, cysteine, 3-sulfydryl propane sulfonic acid etc.

Contain at polymer of the present invention under the situation of part-structure of above-mentioned general formula (3) or (4) expression, can also contain can with the monomer of the vinyl of the part-structure copolymerization of above-mentioned general formula (3) or (4) expression.

Object lesson as the monomer of above-mentioned vinyl is listed below.

For example specifiable is (methyl) alkyl acrylate [for example, (methyl) acrylic acid carbon numbers such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester are Arrcostab of 1～18 etc.]; (methyl) acrylic acid cycloalkyl ester [for example (methyl) cyclohexyl acrylate etc.]; (methyl) acrylic acid aryl ester [for example (methyl) phenyl acrylate etc.]; (methyl) acrylic acid aralkyl ester [for example (methyl) benzyl acrylate etc.]; (methyl) alkyl acrylate [(methyl) hydroxy-ethyl acrylate etc.] that replaces; (methyl) acrylic amide [for example (methyl) acrylamide, dimethyl (methyl) acrylamide etc.]; Aromatic vinyl class [for example, styrene, vinyltoluene, AMS etc.]; Vinyl ester [for example vinylacetate, propionate, tertiary ethylene carbonate etc.]; Allyl ester class [for example allyl acetate etc.]; Halogen monomer [for example vinylidene chloride, vinyl chloride etc.]; Vinyl cyanide [for example (methyl) acrylonitrile etc.]; Olefines [for example ethene, propylene etc.] etc.In polymer of the present invention, above-mentioned vinyl monomer can contain a kind, also can contain more than 2 kinds.

Below the preferred object lesson of expression polymer of the present invention (exemplary compounds: P-1～P-34), but the present invention is not limited to these.

(S equivalent 7.23meq/g, I/O value 0.94)

(S equivalent 5.94meq/g, I/O value 1.42)

(S equivalent 6.56meq/g, I/O value 0.98)

(S equivalent 7.18meq/g, I/O value 2.96)

(S equivalent 4.96meq/g, I/O value 2.33)

(S equivalent 7.18meq/g, I/O value 1.17)

(S equivalent 5.47meq/g, I/O value 1.74)

(S equivalent 6.70meq/g, I/O value 1.41)

(S equivalent 5.76meq/g, I/O value 1.79)

(S equivalent 6.88meq/g, I/O value 1.13)

(S equivalent 5.82meq/g, I/O value 1.53)

(S equivalent 6.51meq/g, I/O value 1.08)

(S equivalent 5.07meq/g, I/O value 2.99)

(S equivalent 1.76meq/g, I/O value 2.81)

(S equivalent 1.55meq/g, I/O value 2.33)

(S equivalent 2.55meq/g, I/O value 2.76)

(S equivalent 2.13meq/g, I/O value 2.21)

(S equivalent 7.45meq/g, I/O value 1.57)

(S equivalent 6.40meq/g, I/O value 1.41)

(S equivalent 6.84meq/g, I/O value 2.62)

(S equivalent 536meq/g, I/O value 2.32)

(S equivalent 11.1meq/g, I/O value 1.75)

(S equivalent 3.56meq/g, I/O value 1.37)

(S equivalent 7.45meq/g, I/O value 1.33)

(S equivalent 4.72meq/g, I/O value 2.56)

(S equivalent 5.04meq/g, I/O value 0.76)

(S equivalent 4.92meq/g, I/O value 0.76)

(S equivalent 2.26meq/g, I/O value 1.56)

(S equivalent 4.21meq/g, I/O value 0.89)

(S equivalent 3.63meq/g, I/O value 1.25)

(S equivalent 3.16meq/g, I/O value 0.82)

(S equivalent 3.00meq/g, I/O value 0.96)

(S equivalent 2.51meq/g, I/O value 1.83)

(S equivalent 2.59meq/g, I/O value 1.21)

(S equivalent 6.51meq/g, I/O value 1.08)

The content of polymer of the present invention in ink-receiver layer is preferably 0.01～10g/m ², be preferably 0.05～5g/m especially ²

(particulate)

Preferably contain particulate in the ink-receiver layer of ink jet recording medium of the present invention.

The ink-receiver layer of ink jet recording medium owing to contain particulate, can obtain porous structure, and the absorbent properties of printing ink are improved thus.If particularly the solid component content of this particulate in ink-receiver layer surpasses more than the 50 quality %, more preferably surpass 60 quality %, then can form better porous structure, can obtain to possess the ink jet recording medium of abundant ink absorption, be preferred therefore.Here, the solid component content of so-called particulate in ink-receiver layer is based on the content that composition is calculated beyond the water in the composition that constitutes ink-receiver layer.

The particulate that uses among the present invention is preferably inorganic fine particles, but only otherwise damage effect of the present invention, organic particle also can use.

As above-mentioned organic particle, preferred specifiable is the polymeric microsphere that obtains by emulsion polymerisation, the polymerization of microemulsion class, emulsifier-free polymerization, seeding polymerization, dispersin polymerization, suspension polymerisation etc., specifically can enumerate the powder of polyethylene, polypropylene, polystyrene, polyacrylate, polyamide, silicones, phenolic resins, natural polymer etc., the polymeric microsphere of latex or emulsion form etc.

As above-mentioned inorganic fine particles, specifiable is for example silicon dioxide particles, colloidal silica, titanium dioxide, barium sulfate, calcium silicates, zeolite, kaolin, galapectite, mica, talcum, calcium carbonate, magnesium carbonate, calcium sulfate, plan boehmite, zinc oxide, zinc hydroxide, aluminium oxide, alumina silicate, calcium silicates, magnesium silicate, zirconia, zirconium hydroxide, cerium oxide, lanthana, yittrium oxide etc.Wherein from forming the viewpoint of good porous structure, preferred silicon dioxide particles, colloidal silica, alumina particulate or plan boehmite.Particulate can directly use predecessor, also can use with the state that forms 2 particles.These atomic average primary particle diameter are preferably below 2 μ m, more preferably below 200nm.

Have again, more preferably average primary particle diameter at the colloidal silica below the 30nm, average primary particle diameter alumina particulate or the average pore radius plan boehmite that is 2～15nm below 20nm, preferred especially silicon dioxide particles, alumina particulate, is intended boehmite at the silicon dioxide particles below the 20nm, average primary particle diameter.

Silicon dioxide particles roughly is divided into damp process particle and dry process (vapor phase method) particle according to its manufacture method usually.In the above-mentioned damp process, main use be decompose by the acid of silicate generate active silica, suitably polymerization and aggegation sedimentation obtain the method for aqueous silicon dioxide to make it.On the other hand, vapor phase method mainly is the method (flame hydrolysis) by the high temperature vapor phase hydrolysis of silicon halide, perhaps silicon sand and coke are passed through with the method (arc process) of air with its oxidation by the reduction and gaseous back of electric arc heated in electric furnace, obtain the method for anhydride silica, so-called " fumed silica " is meant the anhydride silica particulate that obtains by this vapor phase method.As the silicon dioxide particles that uses among the present invention, be preferably the fumed silica particulate especially.

Above-mentioned fumed silica and aqueous silicon dioxide in the density of the silanol group on surface, have or not aspects such as emptying aperture different, thereby show different character, but be suitable for forming the high three-dimensional structure of voidage.Its reason is also indeterminate, but can infer under the situation of aqueous silicon dioxide, and the density of silanol group is up to 5～8/nm on the particulate surface ², silicon dioxide particles is closely aggegation (gathering) easily, and under the situation of fumed silica, the density of silanol group is 2～3/nm on the particulate surface on the other hand ², less, become loose soft aggegation (flocculation) thus, the result becomes the high structure of voidage.

Above-mentioned fumed silica has following feature, because specific area is big especially, so the efficient height of ink absorption, maintenance printing ink, and because refractive index is low, if be dispersed into suitable particle diameter then can give the receiving layer transparency, can obtain high color density and good color emissivity.The transparent this point of receiving layer is not only in the purposes of the requirement transparencys such as OHP, and under the situation that is applicable to paper used for recording such as photograph glossy paper, from obtaining the viewpoint of high color density and good color emissivity gloss, also is very important.

As the average primary particle diameter of above-mentioned fumed silica, be preferably below the 30nm, more preferably below the 20nm, be preferably especially below the 10nm, most preferably be 3～10nm.With regard to above-mentioned fumed silica, by the hydrogen bond that is produced by silanol group, absorption mutually easily between the particle is therefore under average primary particle diameter is situation below the 30nm, the big structure of voidage can be formed, and the absorption of inks characteristic can be improved effectively.

In addition, silicon dioxide granule also can use simultaneously with above-mentioned other particulates.Use at the same time under the situation of these other particulates and above-mentioned fumed silica, the content of fumed silica is preferably more than 30 quality %, more preferably more than 50 quality % in whole particulates.

As the inorganic fine particles of using among the present invention, be preferably alumina particulate, hydrated alumina, these mixture or compound.Wherein, therefore hydrated alumina is preferred owing to can absorb well and fixing printing ink, particularly preferably is and intends boehmite (Al ₂O ₃NH ₂O).Hydrated alumina can use various forms, but from can the easy angle that obtains level and smooth layer in ground considering that the boehmite that preferably uses the colloidal sol shape is as raw material.

For the pore structure of intending boehmite, its average pore radius is preferably 1～30nm, more preferably 2～15nm.In addition, its pore volume is preferably 0.3～2.0cc/g, more preferably 0.5～1.5cc/g.Here, the mensuration of above-mentioned pore radius and pore volume can be undertaken by the nitrogen adsorption desorption method, for example can use gas absorption desorb analyzer (for example trade name " オ system ニ ソ-プ 369 " of コ-Le -company's manufacturing) to measure.

In addition, in alumina particulate, the specific area of vapor phase method alumina particulate is big, and is therefore preferred.The average primary particle diameter of this vapor phase method aluminium oxide is preferably below 30nm, more preferably below 20nm.

Above-mentioned particulate is being used under the situation of ink jet recording medium, also can be for example to open the spy flat 10-81064 number, with 10-119423 number, with 10-157277 number, with 10-217601 number, with 11-348409 number, the spy opens 2001-138621 number, with 2000-43401 number, with 2000-211235 number, with 2000-309157 number, with 2001-96897 number, with 2001-138627 number, Te Kaiping 11-91242 number, with 8-2087 number, with 8-2090 number, with 8-2091 number, with 8-2093 number, with 8-174992 number, with 11-192777 number, the spy opens and waits that disclosed mode is suitable in the communique for 2001-301314 number.

(water-soluble resin)

In the ink-receiver layer of ink jet recording medium of the present invention, preferably also contain water-soluble resin.

As this water-soluble resin, specifiable is that the resin that for example contains hydroxyl as the hydrophilic structure unit is a polyvinyl alcohol resin [polyvinyl alcohol (PVA); the acetoacetyl modified polyvinylalcohol; cation-modified polyvinyl alcohol; anion-modified polyvinyl alcohol; the silanol modified polyvinylalcohol; Pioloform, polyvinyl acetal etc.]; cellulosic resin [methylcellulose (MC); ethyl cellulose (EC); hydroxyethylcellulose (HEC); carboxymethyl cellulose (CMC); hydroxypropyl cellulose (HPC); HEMC; hydroxypropyl methylcellulose etc.]; the chitin class; the shitosan class; starch; resin [the PEO (PEO) that contains ehter bond; PPOX (PPO); polyethylene glycol (PEG); polyvinylether (PVE) etc.]; resin [the polyacrylamide (PAAM) that contains carbamoyl; PVP (PVP); polyacrylic hydrazide etc.] etc.

In addition, also can enumerate the polyacrylate that contains carboxyl as disassociation property group, maleic acid resin, alginate, gelatin class etc.

More than in the middle of, special preferably polyethylene alcohol resinoid.As the example of this polyvinyl alcohol, can enumerate special fair 4-52786 number, special fair 5-67432 number, special fair 7-29479 number, No. the 2537827th, patent, special fair 7-57553 number, No. the 2502998th, patent, No. the 3053231st, patent, the spy opens clear 63-176173 number, No. the 2604367th, patent, Te Kaiping 7-276787 number, Te Kaiping 9-207425 number, Te Kaiping 11-58941 number, the spy opens 2000-135858 number, the spy opens 2001-205924 number, the spy opens 2001-287444 number, the spy opens clear 62-278080 number, Te Kaiping 9-39373 number, No. the 2750433rd, patent, the spy opens 2000-158801 number, the spy opens 2001-213045 number, the spy opens 2001-328345 number, Te Kaiping 8-324105 number, the polyvinyl alcohol of putting down in writing in the Te Kaiping 11-348417 grade etc.

In addition, as the example of the water-soluble resin beyond the polyvinyl alcohol resin, also can enumerate the compound etc. that the spy opens record in the flat 11-165461 communique 0011～0014.

These water-soluble resins can use separately separately, also can use simultaneously more than 2 kinds.

As the content of water-soluble resin of the present invention, with respect to the total solid composition quality of ink-receiver layer, be preferably 9～40 quality %, more preferably 12～33 quality %.

The above-mentioned water-soluble resin of main composition ink-receiver layer of the present invention and above-mentioned particulate can be single raw material separately, also can use the mixed system of a plurality of raw materials.

In addition, from keeping the viewpoint of the transparency, particularly the kind of the water-soluble resin of silicon dioxide particles combination is extremely important with particulate.State in the use under the situation of fumed silica, as this water-soluble resin, be preferably polyvinyl alcohol resin, wherein more preferably saponification degree is 70～100% polyvinyl alcohol resin, and preferred especially saponification degree is 80～99.5% polyvinyl alcohol resin.

Above-mentioned polyvinyl alcohol resin, in its construction unit, contain hydroxyl, because the silanol group on this hydroxyl and above-mentioned silicon dioxide particles surface forms hydrogen bond, therefore the offspring that forms with silicon dioxide particles easily is the three dimensional network pore structure of mesh chain element.Can think that by forming this three dimensional network pore structure it is high and have an ink-receiver layer of the porous structure of sufficient intensity to form voidage.

In ink mist recording, the ink-receiver layer of the porous matter that obtains according to the method described above can absorb printing ink apace by capillarity, can form the just round good point of property that printing ink oozes profit does not take place.

In addition, polyvinyl alcohol resin also can use simultaneously with above-mentioned other water-soluble resins.Use at the same time under the situation of other water-soluble resins and above-mentioned polyvinyl alcohol resin, the content of polyvinyl alcohol resin is preferably more than 50 quality %, more preferably more than 70 quality % in the whole water-soluble resin.

The content ratio of＜particulate and water-soluble resin 〉

The mass ratio of particulate (x) and water-soluble resin (y) [PB is than (x/y)] brings bigger influence also can for the membrane structure and the film-strength of printing ink receiving layer.That is, if mass ratio [PB ratio] becomes big, then voidage, pore volume, surface area (per unit mass) become big, but density and intensity have the tendency of reduction.

From prevent owing to this PB than excessive reduction that causes film-strength and the crackle when dry, prevent from simultaneously this hole to be stopped up easily by resin owing to this PB value is too small, and voidage being reduced and the viewpoint that causes ink absorption to reduce, above-mentioned mass ratio in the ink-receiver layer of the present invention [PB is than (x/y)] is preferably 1.5～10.

By under the situation of ink-jet printer conveyance system,, therefore need ink-receiver layer to have enough film-strengths owing to meeting applied stress on the paper used for recording.Be processed under the situation of sheet in cutting in addition, from the cracking that prevents ink-receiver layer with the aspect such as peel off, also need ink-receiver layer to have enough film-strengths.Consider these situations, above-mentioned mass ratio (x/y) is more preferably below 5, on the other hand from guarantee the viewpoint of high speed ink absorption ink-jet printer, more preferably more than 2.

For example to be fumed silica particulate below the 20nm and water-soluble resin with average primary particle diameter be dispersed in the aqueous solution fully with 2～5 mass ratio (x/y) forms coating liquid, afterwards this coating liquid is coated on the supporter, and under the situation of dry this coat, can form with the offspring of silicon dioxide particles three dimensional network pore structure as the mesh chain, can form the multiple aperture plasma membrane of light transmission at an easy rate, its average fine pore is below 30nm, voidage is 50～80%, the pore specific volume is more than 0.5ml/g, and specific area is at 100m ²More than/the g.

(crosslinking agent)

The ink-receiver layer of ink jet recording medium of the present invention is preferably, the porous layer that the cross linking reaction and solidification of the coat that contain particulate and water-soluble resin, also contains crosslinking agent that can crosslinked this water-soluble resin by this crosslinking agent and water-soluble resin forms.

For crosslinked above-mentioned water-soluble resin, particularly polyvinyl alcohol resin, preferred boron compound.As this boron compound, specifiable is borax, boric acid, borate (for example ortho-borate, InBO for example ₃, ScBO ₃, YBO ₃, LaBO ₃, Mg ₃(BO ₃) ₂, Co ₃(BO ₃) ₂, biborate (Mg for example ₂B ₂O ₅, Co ₂B ₂O ₅), metaborate (LiBO for example ₂, Ca (BO ₂) ₂, NaBO ₂, KBO ₂), tetraborate (Na for example ₂B ₄O ₇10H ₂O), pentaborate (KB for example ₅O ₈4H ₂O, Ca ₂B ₆O ₁₁7H ₂O, CsB ₅O ₅) etc.Wherein from causing the viewpoint of cross-linking reaction fast, preferred borax, boric acid, borate, special preferred boric acid.

As the crosslinking agent of above-mentioned water-soluble resin, also can use boron compound following compound in addition.

Aldehyde compounds such as formaldehyde, glyoxal, glutaraldehyde for example; Ketone compounds such as diacetyl, cyclopentanedione; Two (2-chloroethyl ureas), 2-hydroxyl-4,6-two chloro-1,3,5-triazines, 2,4-two chloro-6-S-triazine sodium salt isoreactivity halide; Divinyl sulfonic acid, 1,3-vinylsulfonyl-2-propyl alcohol, N, N '-ethylenebis (vinylsulfonyl acetamide), 1,3,5-triacryl-six hydrogen-S-triazine isoreactivity vinyl compound; N-such as dimethylol urea, methylol dimethyl hydantion methylol compound; Melmac (for example melamine methylol, alkylation melamine methylol); Epoxy resin;

1, isocyanate ester compounds such as 6-HDI; No. the 3017280th, US Patent specification, with the aziridine compounds of record in No. 2983611; The carboxylic imide analog compounds of record in No. the 3100704th, the US Patent specification; Epoxy compounds such as T 55; 1,6-hexa-methylene-N, N '-second such as diethylidene urea are embraced imine compound; Halogenation such as mucochloric acid, glue phenoxy chloric acid carboxyl aldehyde compound; 2, dioxane compounds such as 3-Er Qiang Ji diox; Containing metal compounds such as lactic acid titanium, aluminum sulfate, chrome alum chromalum, potassium alum, acetic acid zirconium, chromic acetate, polyamine compounds such as tetren, hydrazide compounds such as adipic dihydrazide contain 2 with the low molecule of last oxazoline group or polymer etc.

Above-mentioned crosslinking agent can use independent a kind, also can make up use more than 2 kinds.

Crosslinking curing preferably carries out in the following way: to the coating liquid that contains particulate, water-soluble resin etc. (below be sometimes referred to as " coating liquid A ") or/and add crosslinking agent in the following alkaline solution, and (1) apply above-mentioned coating liquid form coat in, (2) apply in the dry way of the coat that above-mentioned coating liquid forms and this coat show falling rate of drying before whenever, pH is surpassed 7 alkaline solution (below be sometimes referred to as " coating liquid B ") is provided in the above-mentioned coat.Above-mentioned crosslinking agent to provide with the boron compound be that example is preferably carried out according to following method.Promptly, when ink-receiver layer is to make to apply to contain particulate, contain under the situation of the formed layer of coat crosslinking curing that the coating liquid (coating liquid A) of the water-soluble resin of polyvinyl alcohol forms, crosslinking curing can by when (1) applies above-mentioned coating liquid, (2) apply in the dry way of the coat that above-mentioned coating liquid forms and whenever this coat shows before falling rate of drying, pH is surpassed 7 alkaline solution (coating liquid B) is provided in the above-mentioned coat and carries out.Can be contained among either party of coating liquid A or coating liquid B as the boron compound of crosslinking agent, also can in coating liquid A and coating liquid B, all contain.

The consumption of crosslinking agent is preferably 1～50 quality % with respect to water-soluble resin, more preferably 5～40 quality %.

＜mordant 〉

In the present invention, for the resistance to water that further improves formed image and anti-through the time ooze profit, preferably in ink-receiver layer, contain mordant in advance.

As the preferred organic mordant of such mordant is cation property copolymer (cationic mordant) or inorganic mordant, by this mordant is present in the ink-receiver layer, can be with the interaction of the aqueous printing ink that contains as the look material with the anionic property dyestuff and make look material stabilisation, thus can improve resistance to water and anti-through the time ooze profit.Organic mordant and inorganic mordant can be used separately separately, also can use organic mordant and inorganic mordant simultaneously.

As above-mentioned cationic mordant, the general use contained primary～tertiary amine groups or the quaternary ammonium salt group polymer mordant as the cationic group.On the other hand, also can use the non-polymer mordant of cationic among the present invention.

As above-mentioned polymer mordant, can enumerate can be as the copolymer of the homopolymers of the monomer that contains primary～tertiary amine groups and salt thereof or quaternary ammonium salt group (mordant dyeing monomer) or this mordant dyeing monomer and other monomers (hereinafter referred to as " non-mordant dyeing monomer ") or condensation polymer and the mordant that obtains.In addition, these polymer mordant also can be used with any form such as water-soluble polymer or water dispersible latex particle.

As above-mentioned monomer (mordant dyeing monomer), specifiable is trimethyl-to vinyl benzyl chlorination ammonium for example, a trimethyl-vinyl benzyl chlorination ammonium, triethyl group-to vinyl benzyl chlorination ammonium, a triethyl group-vinyl benzyl chlorination ammonium, N, N-dimethyl-N-ethyl-N-is to vinyl benzyl chlorination ammonium, N, N-diethyl-N-methyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-n-pro-pyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-n-octyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-benzyl-N-is to vinyl benzyl chlorination ammonium, N, N-diethyl-N-benzyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-(4-methyl) benzyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-phenyl-N-is to vinyl benzyl chlorination ammonium;

Trimethyl-to the vinyl benzyl ammonium bromide, a trimethyl-vinyl benzyl ammonium bromide, trimethyl-to the vinyl benzyl ichthyodin, a trimethyl-vinyl benzyl ichthyodin, trimethyl-to the vinyl benzyl ammonium acetate, a trimethyl-vinyl benzyl ammonium acetate, N, N, N-triethyl group-N-2-(4-ethenylphenyl) ethyl ammonium chloride, N, N, N-triethyl group-N-2-(3-ethenylphenyl) ethyl ammonium chloride, N, N-diethyl-N-methyl-N-2-(4-ethenylphenyl) ethyl ammonium chloride, N, N-diethyl-N-methyl-N-2-(4-ethenylphenyl) ethyl ammonium acetate;

(methyl) acrylic acid N, N-dimethylaminoethyl, (methyl) acrylic acid N, N-lignocaine ethyl ester, (methyl) acrylic acid N, N-dimethylamino propyl ester, (methyl) acrylic acid N, N-lignocaine propyl ester, N, N-dimethylaminoethyl (methyl) acrylamide, N, N-diethyllaminoethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, N, N-lignocaine propyl group (methyl) acrylamide and salt thereof (for example hydrochloride, nitrate, acetate, lactate, mesylate, tosilate etc.);

Trimethyl-2-(methacryloxy) ethyl ammonium chloride, triethyl group-2-(methacryloxy) ethyl ammonium chloride, trimethyl-2-(acryloxy) ethyl ammonium chloride, triethyl group-2-(acryloxy) ethyl ammonium chloride, trimethyl-3-(methacryloxy) propyl ammonium chloride, triethyl group-3-(methacryloxy) propyl ammonium chloride, trimethyl-2-(methacrylamido) ethyl ammonium chloride, triethyl group-2-(methacrylamido) ethyl ammonium chloride, trimethyl-2-(acrylamido) ethyl ammonium chloride, triethyl group-2-(acrylamido) ethyl ammonium chloride, trimethyl-3-(methacrylamido) propyl ammonium chloride, triethyl group-3-(methacrylamido) propyl ammonium chloride, trimethyl-3-(acrylamido) propyl ammonium chloride, triethyl group-3-(acrylamido) propyl ammonium chloride;

N, N-dimethyl-N-ethyl-2-(methacryloxy) ethyl ammonium chloride, N, N-diethyl-N-methyl-2-(methacryloxy) ethyl ammonium chloride, N, N-dimethyl-N-ethyl-3-(acrylamido) propyl ammonium chloride, trimethyl-2-(methacryloxy) ethyl ammonium bromide, trimethyl-3-(acrylamido) propyl group ammonium bromide, trimethyl-2-(methacryloxy) ethylsulfonic acid ammonium, trimethyl-3-(acrylamido) propyl group ammonium acetate etc.

In addition, also can enumerate N-vinyl imidazole, N-vinyl-glyoxal ethyline, 2-vinylpyridine, 4-vinylpridine, 4-vinyl-N-methyl chloro-pyridine, 4-vinyl-N-ethyl pyridine bromide, dimethyl diallyl ammonium chloride, monomethyl diallyl ammonium chloride etc. as the mordant dyeing monomer.

But these mordant dyeing monomers can use using more than 2 kinds of a kind or combination copolymerization separately.

So-called above-mentioned non-mordant dyeing monomer is meant and does not contain primary～tertiary amine groups and alkalescence or cationic parts such as salt or quaternary ammonium salt group, and show with jetted ink in the interaction or the very little in fact monomer that interacts of dyestuff.

As above-mentioned non-mordant dyeing monomer, specifiable is (methyl) alkyl acrylate [(methyl) methyl acrylate for example for example, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid C1-18 Arrcostabs such as (methyl) stearyl acrylate ester etc.], (methyl) acrylic acid cycloalkyl ester [(methyl) cyclohexyl acrylate etc.], (methyl) acrylic acid aryl ester [(methyl) phenyl acrylate etc.], aralkyl ester [(methyl) benzyl acrylate etc.], (methyl) alkyl acrylate that replaces [(methyl) acrylic acid 2-hydroxyl ethyl ester for example, (methyl) acrylic acid methoxyl group methyl esters, (methyl) allyl acrylate etc.], (methyl) acrylic amide [(methyl) acrylamide for example, dimethyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide etc.], aromatic vinyl base class [styrene, vinyltoluene, AMS etc.], vinyl esters [vinylacetate, propionate, tertiary ethylene carbonate etc.], allyl ester class [allyl acetate etc.], Halogen monomer [vinylidene chloride, vinyl chloride etc.], vinyl cyanide [(methyl) acrylonitrile etc.], olefines [ethene, propylene etc.] etc.

These non-mordant dyeing monomers can be independent a kind or make up more than 2 kinds and use.

In addition, as above-mentioned polymer mordant, also can enumerate poly-second and embrace imines (and derivative), polyvinylamine (and derivative), polyallylamine (and derivative), poly-amidine, cationic polysaccharide (cationic starch, shitosan), two cyanogen cationoid resin (for example dicyandiamide-formalin condensation polymer), polyamine cationoid resin (dicyandiamide-diethylenetriamines condensation polymer), epoxychloropropane-dimethylamine addition polymers, dimethyl diallyl ammonium chloride-sulfur dioxide copolymer etc.

As the organic mordant among the present invention, the polymer that preferably contains quaternary ammonium salt group, special preferable weight-average molecular weight are 1000～100000 (methyl) acrylic polymer, vinyl benzyl ammonium base polymer or the diallyl ammonium base polymer that contain quaternary ammonium salt group.

As mordant of the present invention, also can use inorganic mordant, can enumerate the water-soluble metal salt or the hydrophobic metals salt compound of multivalence as inorganic mordant.

As the object lesson of inorganic mordant, specifiable is salt or the complex that for example is selected from the metal of magnesium, aluminium, calcium, scandium, titanium, vanadium, manganese, iron, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, indium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, hafnium, tungsten, bismuth.

Concrete specifiable be calcium acetate for example, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, formic acid manganese dihydrate, the ammonium manganous sulfate hexahydrate, stannous chloride, ammonium chloride copper (II) dihydrate, copper sulphate, cobalt chloride, cobalt thiocyanate, cobaltous sulfate, the nickel sulfate hexahydrate compound, nickel chloride hexahydrate, the nickel acetate tetrahydrate, the ammonium nickel sulfate hexahydrate, amide groups nickelous sulfate tetrahydrate, aluminum sulfate, al alum, the many aluminium hydroxides of alkalescence, aluminium sulfite, thiosulfuric acid aluminium, aluminium polychloride, the aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, frerrous chloride, iron chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, the zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetone, the lactic acid titanium, the acetylacetone,2,4-pentanedione zirconium, the acetic acid zirconium, zirconium sulfate, zirconium carbonate ammonium, zirconium stearate, zirconium caprylate, zirconium nitrate, basic zirconium chloride, zirconyl hydroxychloride, chromic acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, the magnesium citrate nonahydrate, sodium phosphotungstate, natrium citricum tungsten, 12 tungstophosphoric acid n hydrates, 12 tungstosilicic acids, 26 hydrates, molybdenum chloride, 12 molybdophosphate n hydrates, gallium nitrate, nitric acid germanium, strontium nitrate, the acetic acid yttrium, yttrium chloride, yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, the benzoic acid lanthanum, cerium chloride, cerous sulfate, cerium octoate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, bismuth nitrate etc.

As inorganic mordant of the present invention, be preferably water miscible multivalent metal salt, more preferably aluminum contained compound, titanium-containing compound, zirconium-containing compound are preferably alkaline many aluminium hydroxide, aluminium polychloride, aluminum acetate, aluctyl, lactic acid titanium, acetic acid zirconium, zirconium carbonate ammonium, basic zirconium chloride especially.

In the present invention, the above-mentioned mordant dyeing dosage that contains in the ink-receiver layer is preferably 0.01g/m ²～10g/m ², 0.1g/m more preferably ²～5g/m ²

In the present invention, ink-receiver layer preferably contains surfactant with coating liquid (coating liquid A).Can use in cationic, anionic species, nonionic class, both sexes, fluorine class, the silicon class surfactant any as this surfactant.

As above-mentioned nonionic class surfactant, specifiable is polyoxyalkylene alkyl ether and polyoxy alkylidene alkyl phenyl ethers (diethylene glycol (DEG) monoethyl ether for example, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylplenyl ether etc.), the oxirane propylene oxide block copolymer, sorbitan fatty acid ester class (sorbitan one laurate ester for example, the anhydrosorbitol monooleate ester, sorbitan trioleate etc.), polyoxyethylene sorbitan fatty acid ester class (polyoxyethylene sorbitol acid anhydride one laurate ester for example, polyoxyethylene sorbitol acid anhydride monooleate, Tween-85 etc.), polyoxyethylene sorbitol fatty acid ester (for example four oleic acid polyoxyethylene sorbitol esters etc.), fatty acid glyceride class (for example monoolein etc.), polyoxyethylene fatty acid glyceride class (monostearate polyoxyethylene glyceride, monooleate polyoxyethylene glyceride etc.), polyoxyethylene fatty acid ester class (polyethylene glycol one laurate ester, polyethylene glycol monooleate etc.), polyoxyethylene alkyl amine, acetylenic glycol class (for example 2,4,7,9-tetramethyl-5-decine-4, the ethylene oxide adduct of 7-glycol and this glycol, propylene oxide adduct etc.) etc., wherein preferred polyoxyalkylene alkyl ether class.This nonionic class surfactant can be used for coating liquid A and coating liquid B.In addition, above-mentioned nonionic class surfactant can use separately, also can make up more than 2 kinds and use.

As above-mentioned amphoteric surfactant, specifiable is amino acid pattern, carboxyl ammonium betaine type, sulfo group ammonium betaine type, ammonium sulfuric ester betaine type, imidazoles betaine type etc., for example can use United States Patent (USP) No. 3843368 specification, spy open clear 59-49535 communique, with 63-236546 communique, spy open flat 5-303205 communique, with the 8-262742 communique, with the surfactant of record in the 10-282619 communique etc.As this amphoteric surfactant; preferred amino acid type amphoteric surfactant; as this amino acid type amphoteric surfactant; the specifiable material of putting down in writing, for example being derived by amino acid (glycine, glutamic acid, histidine etc.) of opening in the flat 5-303205 communique as the spy, concrete specifiable is acid of N-aminoacyl and the salt thereof that imports long acyl.Above-mentioned amphoteric surfactant can use a kind, also can make up more than 2 kinds and use.

As above-mentioned anionic species surfactant, specifiable is soap (for example odium stearate, potassium oleate), alkyl sulfate salt (for example sodium lauryl sulfate, bay sulfuric ester triethanol ammonium), sulfonate (for example neopelex), alkyl sulfo succinate (for example dioctyl bay sodium succinate), alkyl diphenyl base ether disulfonate, alkylphosphonic etc.

As above-mentioned cationic surfactant, specifiable is alkylamine salt, quaternary ammonium salt, pyridiniujm, imidazole salts etc.

As above-mentioned fluorine class surfactant, the specifiable methods such as electrofluorination, telomerisation, oligomerization that are to use are through the intermediate that has perfluoroalkyl and derived compounds.

Specifiable is for example fluorinated alkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trialkyl ammonium salts, the oligomer that contains perfluoroalkyl, perfluoralkyl phosphate etc.

As above-mentioned silicon class surfactant, be preferably silicone oil with the organic group modification, can form like this with the structure of organic group modified siloxane structure side chain, the structure of modification two ends, the structure of modification one side end.As the organic group modification, specifiable is amino modified, polyether-modified, epoxide modified, carboxy-modified, methyl alcohol modification, alkyl-modified, aralkyl modification, phenol-modified, fluorine modification etc.

As the content of surfactant among the present invention, the coating liquid of using with respect to ink-receiver layer (coating liquid A) is preferably 0.001～2.0%, and more preferably 0.01～1.0%.In addition, under the situation of using the above ink-receiver layer coating liquid of 2 liquid to apply, preferably in each coating liquid, add surfactant.

In the present invention, ink-receiver layer preferably contains to be useful on and prevents the high boiling organic solvent that curls.Above-mentioned high boiling organic solvent is that boiling point is water-soluble or hydrophobic compound at the organic compound more than 150 ℃ under normal pressure.These at room temperature can be that liquid also can be solid, can be that low molecule also can be a macromolecule.

Concrete specifiable be aromatic carboxylic acid esters's (dibutyl phthalate for example, diphenyl phthalate, benzoic acid phenyl ester etc.), aliphatic carboxylic acid esters,'s class (dioctyl adipate for example, dibutyl sebacate, methyl stearate, dibutyl maleate, dibutyl fumarate, ATEC etc.), phosphoric acid ester (trioctyl phosphate for example, tricresyl phosphate etc.), epoxies (epoxidised soybean oil for example, epoxidized fatty acid methyl esters etc.), alcohols (stearyl alcohol for example, ethylene glycol, propane diols, diethylene glycol (DEG), triethylene glycol, glycerine, diethylene glycol-butyl ether (DEGMBE), triethylene glycol monobutyl ether, the glycerine monomethyl ether, 1,2, the 3-butantriol, 1,2, the 4-butantriol, 1,2,4-penta triol, 1,2, the 6-hexanetriol, sulphur support diethanol, triethanolamine, polyethylene glycol etc.), vegetable oil (soybean oil for example, the sunflower seed wet goods), senior aliphatic carboxylic acid (linoleic acid for example, oleic acid etc.) etc.

＜supporter 〉

As the supporter that uses among the present invention, any in the opaque supporter that can use the transparent supporting body that constitutes by transparent materials such as plastics, constitutes by opaque materials such as paper.From applying flexibly the transparent aspect of ink-receiver layer, preferably use the opaque supporter of transparent supporting body or high-luster.Also can use Worm type optical disks such as read-only optical discs such as CD-ROM, DVD-ROM, CD-R, DVD-R in addition, can write the type CD as supporter in addition, at the additional ink-receiver layer of label surface side.

As operable material on the above-mentioned transparent supporting body, preferably have the transparency, can bear the material of the photothermal character when in OHP or back of the body irradiation display, using.As this material, specifiable is PET polyesters such as (PET) for example; Polysulfones, polyphenylene oxide, polyimides, Merlon, polyamide etc.Preferred polyester class wherein, preferred especially PET.

Thickness to above-mentioned transparent supporting body is not particularly limited, but preferred 50～200 μ m are considered in calm aspect easy to operate.

As the opaque supporter of high-luster, the material that a side surface of ink-receiver layer has 40% above glossiness can be set preferably.The value of above-mentioned glossiness for trying to achieve according to the method for record among the JIS P-8142 (75 degree mirror surface luster test methods of paper and paperboard).Specifically can enumerate following supporter.

Specifiable be for example art paper, coated paper, casting coated paper, silver halide photography with the paper supporter of the high-lusters such as barium monoxide paper that use in the supporter etc.; PET polyesters such as (PET); Cellulose esters such as celluloid, cellulose acetate, cellulose acetate-butyrate; Contain the film that Chinese white etc. becomes the high-luster of opaque (surface can be carried out press polish and be handled) in the plastic sheetings such as polysulfones, polyphenylene oxide, polyimides, Merlon, polyamide; Perhaps at above-mentioned various paper supporters, above-mentioned transparent supporting body or contain supporter that the polyolefin coated layer that contains or do not contain Chinese white is set on the film surface of high-luster of Chinese white etc. etc.

Also can compatibly enumerate the expanded polyester film (for example containing polyolefin fine particle) that contains Chinese white by extending to form the foaming PET in space.Have, the cold coating paper that uses in the sensitive paper that silver halide photography is used also can be suitable for again.

Thickness to above-mentioned opaque supporter also is not particularly limited, but preferred 50～300 μ m are considered in calm aspect easy to operate.

In addition, in order to improve wetting characteristics and caking property, also can use the supporter of on above-mentioned supporting body surface, implementing Corona discharge Treatment, glow discharge processing, flame treatment, ultraviolet treatment with irradiation etc.

Be described in detail at the body paper that uses in the above-mentioned cold coating paper below.

As above-mentioned body paper, be primary raw material with the wood pulp, use synthetic fibers such as synthetic pulps such as polypropylene or nylon or polyester and wood pulp together to carry out papermaking as required.As above-mentioned wood pulp, can use any among LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, the NUKP, but preferred short fiber component many LBKP, NBSP, LBSP, NDP, the LDP of using morely.

Wherein, LBSP or/and the ratio of LDP preferably more than the 10 quality %, below the 70 quality %.

Above-mentioned slurry preferably uses the few chemical pulp of impurity (NBSK or sulfurous wintercherry), handles the slurry that has improved whiteness by bleaching and also can use.

Can suitably add sizing agents such as higher fatty acids, alkyl ketene dimer in the body paper, Chinese whites such as calcium carbonate, talcum, titanium oxide, softening agents such as water retention agent, dispersant, quaternary ammonium such as paper power reinforcing agent, fluorescent whitening agent, polyvinyl alcohol such as starch, polyacrylamide, polyvinyl alcohol etc.

The beating degree of the slurry that uses in the papermaking is preferably 200～500ml according to the regulation of CSF, with regard to the fibre length after the making beating, is preferably 30～70% according to 24 order residual components quality % that stipulate among the JIS P-8207 and 42 order residual components quality % sums in addition.In addition, the quality % of 4 order residual components is preferably below 20 quality %.

The weight of body paper is preferably 30～250g, is preferably 50～200g especially.The thickness of body paper is preferably 40～250 μ m.Body paper also can carry out the press polish processing and give its high flatness after papermaking stage or papermaking.Body paper density is generally 0.7～1.2g/m ²(JIS P-8118).

Have, body paper rigidity is preferably 20～200g under the defined terms in according to JIS P-8143 again.

Also can the coating surface sizing agent on the body paper surface, as surperficial sizing agent can use with above-mentioned body paper in the identical sizing agent that can add.

The pH of body paper is preferably 5～9 under the situation that water hot extraction's method of stipulating is measured in by JIS P-8113.

Applying the polyethylene of body paper surface and the inside, mainly is low density polyethylene (LDPE) (LDPE) or/and high density polyethylene (HDPE) (HDPE), but also can use other LLDPE and polypropylene etc. of a part.

Particularly form the polyethylene layer of a side of ink-receiver layer, preferably as general implementation on taking a picture with sensitive paper, in polyethylene, add rutile or anatase-type titanium oxide, fluorescent whitening agent, ultramarine, improve opacity, whiteness and tone.Here, the content of titanium oxide preferably approximately is 3～20 quality % with respect to polyethylene, more preferably 4～13 quality %.Thickness to polyethylene layer is not particularly limited, and layer all is preferably 10～50 μ m in the table the inside.Also have,, also priming coat can be set for polyethylene layer being given the adaptation with ink-receiver layer.As this priming coat, be preferably waterborne polyester, gelatin, PVA.In addition, the thickness of this priming coat is preferably 0.01～5 μ m.

Polyethylene coated paper also can be used as glossy paper, when the melt extruded polyethylene applies on the body paper surface in addition, also can use and implement that so-called embossing is handled and the paper that is formed on available delustring face and glassy surface (silky surface) on the common photosensitive paper.

The back coating also can be set on supporter, and as the composition that can add in this back coating, specifiable is Chinese white and aqueous binders, other compositions.

As the Chinese white that the back is contained in the coating, specifiable is precipitated calcium carbonate for example, powdered whiting, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, satin white, alumina silicate, diatomite, calcium silicates, magnesium silicate, synthetic amorphous silicas, colloidal silica, colloidal alumina, intend boehmite, aluminium hydroxide, aluminium oxide, lithopone, zeolite, add endellite, magnesium carbonate, white inorganic pigments such as magnesium hydroxide, styrene plastic pigment, acrylics pigment, polyethylene, microcapsules, Lauxite, organic pigments such as melmac etc.

As the aqueous binders that use in the coating back, specifiable is water dispersible macromolecules such as water soluble polymer, styrene butadiene latices, acrylic emulsion such as styrene/maleate copolymer, styrene/acrylic salt copolymer, polyvinyl alcohol, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, carboxyethyl cellulose, polyvinylpyrrolidone etc. for example.

As other compositions that contain in the coating of back, specifiable is defoamer, foam inhibitor, dyestuff, fluorescent whitening agent, anticorrisive agent, anti-hydrated agent etc.

The making of＜ink jet recording medium 〉

The ink-receiver layer of ink jet recording medium of the present invention, preferably form by the following method: for example on supporting body surface, apply the coating liquid A that contains particulate and water-soluble resin at least, apply simultaneously with this in (1), (2) apply in the dry way of the coat that forms by this and whenever this coat shows before falling rate of drying speed, after providing pH to surpass 7 coating liquid B, make the method for the coat crosslinking curing of accepting this coating liquid B.Here, polymer of the present invention can be contained among at least one side among above-mentioned coating liquid A or the coating liquid B, but from the ink absorption aspect, preferably is contained among the coating liquid A.

In addition, crosslinking agent that can crosslinked above-mentioned water-soluble resin also can be contained among above-mentioned coating liquid A or the coating liquid B among either party.

Setting is finished the ink-receiver layer of crosslinking curing by aforesaid operation, from ink absorption with prevent that viewpoint such as film crack from being preferred.

After above processing, mordant can be present in the established part of ink-receiver layer in a large number, therefore the look material of ink-jet is by fully mordant dyeing, thus can improve color density, through the time ooze resistance to water, the ozone resistance of the writings and image after profit, photographic department are divided gloss, lettering, so be preferred.Part mordant can be contained in the layer that is arranged at first on the supporter, and this moment can be identical with additional afterwards mordant, also can be different.

Among the present invention, the ink-receiver layer that contains particulate (for example fumed silica) and water-soluble resin (for example polyvinyl alcohol) at least for example can be modulated by the following method with coating liquid (coating liquid A).That is,

Xiang Shuizhong adds particulate and dispersants (for example the silicon dioxide particles in the water is 10～20 quality %) such as fumed silica, use and rotate wet type colloid mill (for example " the Network レ ア ミ Star Network ス " of エ system テ Network ニ Star Network (strain) manufacturing) at a high speed, at for example 10000rpm (after disperseing with 20 minutes (preferred 10～30 minutes) under preferred 5000～20000rpm) the high-speed rotating conditions, add polyvinyl alcohol (PVA) aqueous solution (for example being the PVA of 1/3 left and right sides quality of above-mentioned fumed silica), can by with above-mentioned same rotating condition under disperse to modulate.In order to give coating liquid stability, preferably, perhaps use dispersant with about adjusting pH to 9.2 such as ammoniacal liquor.The coating liquid that obtains is the uniform sol state, by being coated on the supporter it and drying with following painting method, can form the ink-receiver layer of the porous matter with three dimensional network pore structure.

In addition, in the modulation of the water dispersion that constitutes by above-mentioned fumed silica and dispersant, can modulate the vapor phase method silica aqueous dispersion in advance, both this aqueous dispersions can be added in the aqueous dispersant afterwards, also aqueous dispersant can be added in the fumed silica aqueous dispersions, also can mix simultaneously.In addition, also can not use the fumed silica aqueous dispersions and use the fumed silica of powder shaped, and add in the aqueous dispersant as described above.

After mixing above-mentioned fumed silica and dispersant, by with dispersion machine with this mixed liquor grain refined, can obtain the aqueous dispersions that average grain diameter is 50～300nm.As the dispersion machine that is used to obtain this aqueous dispersions, can use and rotate known various dispersion machines at present such as dispersion machine, medium agitating type dispersion machine (ball mill, sand mill etc.), ultrasonic dispersing machine, colloidal state grinding dispersion machine, high pressure dispersion machine at a high speed, but from carrying out the aspect of the atomic dispersion of formed pearl effectively, preferable medium agitating type dispersion machine, colloidal state are ground dispersion machine or high pressure dispersion machine.

In addition, as the solvent in each operation, can make water, organic solvent or these mixed solvent.As the organic solvent that can be used for this coating, specifiable is alcohols such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, methoxypropanol, ketones such as acetone, MEK, oxolane, acetonitrile, ethyl acetate, toluene etc.

In addition, in order to improve the dispersiveness of above-mentioned coating liquid, can add dispersant.As dispersant, preferably use above-mentioned cationic resin.

Above-mentioned dispersant is preferably 0.1%～30% with respect to atomic addition, and more preferably 1%～10%.

On the other hand, to the qualification especially of pH of above-mentioned coating liquid, but pH is preferably more than 2, below 6, more preferably more than 3, below 5.By being that coating liquid more than 2, below 6 forms ink-receiver layer by pH, can further suppressing the image that passing in time produces and ooze profit.

This ink-receiver layer is with the coating of coating liquid, known painting method such as can be coated with, pneumatic scraper applies, cutter is coated with, bar is coated with, scraper coating, extrusion coated, oppositely roller coating, rod are coated with by extrusion die and carry out.

When the coating ink-receiver layer is with coating liquid (coating liquid A) or after applying, in this coat, provide coating liquid B, but this coating liquid B can before showing falling rate of drying speed, the coat after the coating provide.That is, after the coating ink-receiver layer is with coating liquid (coating liquid A),, can finish manufacturing very ideally by when this coat shows constant rate of drying speed, importing coating liquid B.In this coating liquid B, can contain mordant.

Here, so-called above-mentioned " coat shows before the falling rate of drying speed " typically refers to and applying the process of ink-receiver layer with a few minutes after the coating liquid, during this period, demonstrate the phenomenon of " constant rate of drying speed " that the content of solvent in the coated coat (decentralized medium) and time reduces pro rata.For showing the time of being somebody's turn to do " constant rate of drying speed ", for example be documented in the chemical engineering handbook (the 707th～712 page, ball kind (strain) distribution, clear and on October 25th, 55).

After applying coating liquid A as described above, be dried to this coat and show falling rate of drying speed, this drying is generally carried out 0.5～10 minute (preferred 0.5～5 minute) under 40～180 ℃.This drying time is certainly according to coated weight and difference, but usually suitably in above-mentioned scope.

As showing the method that provides before the falling rate of drying speed at above-mentioned first coat, specifiable is that (1) is in the further method of coating liquid B, the method that spray by methods such as injections (2), (3) flood the supporter that has formed this coat in coating liquid B the method etc. of applying on the coat.

In said method (1), known painting method such as the painting method that applies coating liquid B, for example can utilize that curtain coating, extrusion die are coated with, pneumatic scraper applies, cutter is coated with, bar is coated with, scraper coating, extrusion coated, oppositely roller coating, rod are coated with.But, the preferred method of utilizing as extrusion die is coated with, coating machine such as curtain coating, rod are coated with does not directly contact with first coat that has formed.

After coating liquid B is provided, generally heated 0.5～30 minute down at 40～180 ℃, carry out drying and curing.Wherein preferably heated 1～20 minute down at 40～150 ℃.

In addition, when applying ink-receiver layer coating liquid (coating liquid A), provide under the situation of above-mentioned coating liquid B, can be by on supporter, applying (multiple layer applies) coating liquid A and coating liquid B simultaneously, and make coating liquid A with after supporter contacts, drying solidify to form ink-receiver layer.

Above-mentioned coating simultaneously (multiple layer applies) can be undertaken by the painting method that uses extrusion die to be coated with machine, episodic curtain coater.After the coating, need carry out drying to the coat that forms simultaneously, drying at this moment generally heats coat down at 40～150 ℃ and carried out in 0.5～10 minute, preferably heats 0.5～5 minute down at 40～100 ℃.

Be coated with by for example extrusion die under the situation of carrying out above-mentioned coating simultaneously (multiple layer applies), Pen Chu two kinds of coating liquids are near the ejiction opening of extrusion die coating machine simultaneously, promptly go forward to form multiple layer moving to supporter, and be coated on the supporter with the multiple layer of this state.When the two-layer coating liquid of lamination is on moving to supporter before applying, on the interface of two liquid cross-linking reaction takes place easily, therefore near the ejiction opening of extrusion die coating machine, the easy hybrid concurrency of two liquid of ejection is given birth to tackify, and this brings influence to applying operation sometimes.Thereby, when applying simultaneously as described above, preferably when applying coating liquid A and coating liquid B, make separation layer liquid (intermediate layer liquid) between above-mentioned two liquid, carry out three layers of coating.

Above-mentioned separation layer liquid can be selected with being not particularly limited.For example can enumerate the aqueous solution that contains the minor amount of water soluble resin or water etc.Above-mentioned water-soluble resin considers coating and uses as tackifier etc., and specifiable is polymer such as cellulosic resin (for example hydroxypropyl methylcellulose, methylcellulose, HEMC etc.), polyvinylpyrrolidone, gelatin for example.In addition, in separation layer liquid, also can contain above-mentioned mordant.

After forming ink-receiver layer on the supporter, by using supercalender, gloss calender etc., add in heating and to implement press polish between depressing by roll spacing and handle, can improve surface smoothing, glossiness, the transparency and strength of coating.Yet the factor (promptly ink absorption reduces sometimes) that becomes voidage sometimes and reduce is handled in this press polish, therefore needs to set voidage and reduces few condition and carry out under this condition.

Roller temperature when handling as the enforcement press polish is preferably 30～150 ℃, more preferably 40～100 ℃.

In addition, the line pressure when handling as press polish between roller is preferably 50～400kg/cm, more preferably 100～200kg/cm.

As the bed thickness of above-mentioned ink-receiver layer, under the situation of ink mist recording,, therefore need decide according to voidage in the layer owing to need have the absorptive capacity that can all absorb drop.Be 8nL/mm for example at quantity of ink ², voidage is under 60% the situation, needing bed thickness is the above films of about 15 μ m.

If consider this point, then under the situation of ink mist recording, be preferably 10～50 μ m as the bed thickness of ink-receiver layer.

In addition, the meta of the fine pore of ink-receiver layer (median) footpath is preferably 0.005～0.030 μ m, more preferably 0.01～0.025 μ m.

Above-mentioned voidage and pore meso-position radius can use mercury porosimeter (trade name " ボ ア サ イ ザ-9320-PC2 " that (strain) Shimadzu Seisakusho Ltd. makes) to measure.

The face pH of ink-receiver layer is preferably more than 3, below 7, more preferably more than 3, below 5 among the present invention.Here, so-called face pH is meant the method for putting down in writing according among the J.TAPPI paper pulp test method No.49, the surface p H that uses distilled water to measure after 30 seconds.If pH more than 3, then can further improve the image keeping quality, if pH can suppress the profit of oozing under the super-humid conditions further 7 with the next resistance to water that can further improve.Thereby, if above-mentioned face pH more than 3, below 7, then can improve further through the time ooze profit, ozone resistance and light resistance.

In addition, ink-receiver layer preferably has the good transparency, and for this reason, the turbidity value when forming ink-receiver layer on the transparent membrane supporter is preferably below 30%, more preferably below 20%.

Above-mentioned turbidity value can use turbidimetric apparatus (HGM-2DP: ス ガ testing machine (strain)) measure.

In the formation layer (for example ink-receiver layer or back coating etc.) of ink jet recording medium of the present invention, can add polymeric microsphere and disperse thing.Using this polymeric microsphere to disperse the purpose of thing is the film rerum naturas such as crack of improving size stabilization, preventing to curl, prevent to bond, prevent film.With regard to polymeric microsphere disperses thing, the spy open clear 62-245258 number, with 62-1316648 number, with on the books in 62-110066 number each communique.In addition, disperse thing, can prevent the crack of layer and curl if in containing the layer of above-mentioned mordant, add the polymeric microsphere of glass transition temperature low (below 40 ℃).In addition, disperse thing, also can prevent to curl if in the coating of back, add the high polymeric microsphere of glass transition temperature.

In addition, ink jet recording medium of the present invention also can according to the spy open flat 10-81064 number, with 10-119423 number, with 10-157277 number, with 10-217601 number, with 11-348409 number, spy open 2001-138621 number, with 2000-43401 number, with 2000-211235 number, with 2000-309157 number, with 2001-96897 number, with 2001-138627 number, spy open flat 11-91242 number, with 8-2087 number, with 8-2090 number, with 8-2091 number, make with the method for putting down in writing in each communique such as 8-2093 number.

[embodiment]

Specifically describe the present invention below by embodiment, but the present invention is not limited to these embodiment.In addition, " part " among the embodiment and " % " are not having to represent " mass parts " and " quality % " under the situation of specified otherwise, " mean molecule quantity " and " degree of polymerization " expression " weight average molecular weight " and " weight average degree of polymerization ".

[synthesis example]

Synthesis example 1

13.5 parts of polybutadiene (NISSO-PB G1000: Japanese Cao Da (strain) manufacturing), 15.6 parts of 2 mercapto ethanols, 2.84 parts of aminoothyl mercaptan hydrochlorides are dissolved in 13.5 parts of ethyl acetate/isopropyl alcohols=1/1wt mixed liquor.Flow down at nitrogen and to be heated to 70 ℃, add 0.062 part 2,2-azo two (2, the 4-methyl pentane nitrile) [the pure medicine of trade name: V-65 and light (strain) manufacturing] adds thermal agitation under 70 ℃.Add 0.062 part of V-65 after 2 hours again, under 70 ℃, added thermal agitation 4 hours.

After wherein adding 128 parts of ion exchange waters equably and making it emulsification, heating up in a steamer desolvates obtains polymer 1 (exemplary compounds: P-6, sulphur equivalent: 7.18meq/g, I/O value: emulsion 1.17).

Synthesis example 2

Except 15.6 parts of 2 mercapto ethanols in the synthesis example 1 being become 21.6 parts of α-thioglycerols, fully similarly obtain polymer 2 (exemplary compounds: P-7, sulphur equivalent: 5.47meq/g, I/O value: the aqueous solution 1.74) with synthesis example 1.

Synthesis example 3

Except 2.84 parts of aminoothyl mercaptans in the synthesis example 1 are become 3.54 parts of N, beyond the N-dimethyl ethanethiol hydrochloride, fully similarly obtain polymer 3 (above-mentioned exemplary compounds: P-10, sulphur equivalent: 6.88meq/g, I/O value: emulsion 1.13) with synthesis example 1.

Synthesis example 4

Except with the consumption of the 2 mercapto ethanol in the synthesis example 3 by 15.6 parts become 7.81 parts, with N, the consumption of N-dimethyl ethanethiol hydrochloride becomes beyond 17.7 parts by 3.54 parts, fully similarly obtain polymer 4 (above-mentioned exemplary compounds: P-9 with synthesis example 3, sulphur equivalent: 5.76meq/g, I/O value: the aqueous solution 1.79).

Synthesis example 5

Except the consumption of the 2 mercapto ethanol in the synthesis example 1 being changed into 17.6 parts and do not add the aminoothyl mercaptan hydrochloride, fully similarly obtain polymer 5 (above-mentioned exemplary compounds: P-1 with synthesis example 1, sulphur equivalent: 7.23meq/g, I/O value: emulsion 0.94).

Synthesis example 6

Except the consumption with the 2 mercapto ethanol in the synthesis example 3 becomes 13.7 parts by 15.6 parts, fully similarly obtain polymer 6 (above-mentioned exemplary compounds: P-12, sulphur equivalent: 6.51meq/g, I/O value: emulsion 1.08) with synthesis example 3.

Synthesis example 7

Except 2.84 parts of aminoothyl mercaptans in the synthesis example 1 being become 4.45 parts of 3-unithiols, fully similarly obtain polymer 7 (exemplary compounds: P-8, sulphur equivalent: 6.70meq/g, I/O value: emulsion 1.41) with synthesis example 1.

Synthesis example 8

10.7 parts of acrylamides, 6.49 parts of pentaerythrites four (mercaptoacetate) are dissolved in 52 parts of ethanol.Flow down at nitrogen and to be heated to 70 ℃, add 0.0745 part 2,2-azo two (2, the 4-methyl pentane nitrile) V-65 added thermal agitation 4 hours under 70 ℃.

Filter the sediment that generates, (molecular weight is different from above-mentioned exemplary compounds: P-16, sulphur equivalent: 3.49meq/g, I/O value: white solid 2.66) to obtain polymer 8.

Synthesis example 9

Except the 6.49 parts of pentaerythrites four (mercaptoacetate) in the synthesis example 8 being become 2.07 part of two (2-mercaptoethyl) ether, (molecular weight is different from above-mentioned exemplary compounds: P-14 fully similarly to obtain polymer 9 with synthesis example 8, sulphur equivalent: 4.70meq/g, I/O value: white solid 2.92).

Synthesis example 10

Except the 6.49 parts of pentaerythrites four (mercaptoacetate) in the synthesis example 8 being become 0.938 part of 2 mercapto ethanol, the comparative example that fully similarly obtains following structural formula with synthesis example 8 is with polymer 10 (sulphur equivalent: 1.27meq/g, I/O value: white solid 3.24).

Polymer 10

Synthesis example 11

Except 10.7 parts of acrylamides in the synthesis example 8 being become 48.8 parts of hydroxy-ethyl acrylates, fully similarly obtain polymer 11 (sulphur equivalent: 1.09meq/g, the I/O value: white solid 1.55) that the comparative example of following structural formula is used with synthesis example 8.

Polymer 11

(making of supporter)

Wood pulp making beating to the Canadian freeness that will be made of 100 parts of LBKP by two Moving plate refiners (double disc refiner) is 300ml, all to add 0.5 part of epoxidation 22 phosphoamide, 1.0 parts of PAMAs, 0.1 part of polyamide polymeric amine epichlorohydrin, 0.5 part of PAMC with respect to the absolute dry weight mass ratio of starching, by the fourdrinier machine weighing, make 170g/m ²Body paper.

In order to adjust the surface size of above-mentioned body paper, in 4% polyvinyl alcohol water solution, add 0.04% fluorescent whitening agent (" Whitex BB " that Sumitomo Chemical (strain) is made), it is immersed in makes in the above-mentioned body paper and become 0.5g/m by the absolute dry weight mass conversion ², implement press polish after the drying again and handle, obtain the basic paper that density is adjusted to 1.05g/ml.

After wire (wire) face (back side) side of the basic paper that obtains carried out Corona discharge Treatment, use the melt extruded machine to apply and make high density polyethylene (HDPE) thickness reach 19 μ m, form the resin bed that constitutes by delustring face (following the resin aspect is called " back side ").Resin bed to this rear side further carries out Corona discharge Treatment, apply then and will be dispersed in dispersion liquid in the water with 1: 2 mass ratio, make dry mass reach 0.2g/m as the aluminium oxide (" alumina sol 100 " that daily output chemical industry (strain) is made) of antistatic additive and silica (" the ス ノ-テ Star Network ス O " of daily output chemical industry (strain) manufacturing) ²

And then, after felt face (surface) side of a side that resin bed is not set implemented Corona discharge Treatment, use the melt extruded machine will contain 10% anatase titanium dioxide, micro-ultramarine and 0.01% (with respect to polyethylene) fluorescent whitening agent, MFR (melt flow rate (MFR)) is 3.8 low density polyethylene (LDPE) extruding, make thickness become 29 μ m, thereby form the thermoplastic resin (following this high glaze face is called " surface ") of high glaze in the face side of basic paper, form supporter.

Embodiment 1

(the ink-receiver layer modulation of coating liquid A)

Mix (1) fumed silica particulate, (2) ion exchange water and (3) " シ ヤ ロ-Le DC-902P " in the following composition, after using KD-P ((strain) シ Application マ Le エ Application -プ ラ イ ゼ ス makes) to disperse, add the solution that contains following (4) zirconium oxyacetate, (5) boric acid water, (6) polyvinyl alcohol, (7) surfactant, (8) polymer 1, (9) ion exchange water, modulation ink-receiver layer coating liquid A.

The mass ratio of silicon dioxide particles and water-soluble resin (PB ratio=(1)/(7)) is 4.5, and ink-receiver layer is 3.5 with the pH of coating liquid A, is acid.

The composition of＜ink-receiver layer coating liquid A 〉

(1) fumed silica particulate (inorganic fine particles) is 10.0 parts

(" the レ オ ロ シ-Le QS-30 " that (strain) ト Network ヤ マ makes, average primary particle diameter is 7nm)

(2) ion exchange water is 51.6 parts

(3) " シ ヤ ロ-Le DC-902P " (51% aqueous solution) 1.0 parts

(dispersant, the first industrial pharmacy (strain) are made)

(4) zirconium oxyacetate (25% aqueous solution) is 0.3 part

(5) boric acid water (5% aqueous solution, crosslinking agent) is 8.0 parts

(6) polyvinyl alcohol (8% aqueous solution, water-soluble resin) is 27.8 parts

(" PVA235 " that (strain) Network ラ レ makes, saponification degree 88%, the degree of polymerization 3500)

(7) surfactant is 0.1 part

(" the エ マ Le ゲ Application 109P " that flower king (strain) makes, 2% aqueous solution, HLB value 13.6)

(8) polymer 1 (25% emulsion) is 2.5 parts

(9) ion exchange water is 23.1 parts

(making of ink jet recording medium (paper))

After carrying out corona discharge on the surface of above-mentioned supporter, on the surface of supporter, use the extrusion die coating machine with 200ml/m ²Coated weight apply the coating liquid A (coating operation) that uses by the above-mentioned ink-receiver layer that obtains, the solid constituent concentration of using air drier to make it to be dried to coat 80 ℃ (wind speed 3～8m/ seconds) becomes 20%.This coat shows constant rate of drying speed in the meantime.Then, be immersed in 30 seconds among the coating liquid B (pH9.3) of following composition at once, make it with 20g/m ²Amount attached to (giving the operation of mordant solution) on this coat, again at 80 ℃ of down dry 10 minutes (drying processes).Make thus and be provided with the ink-jet recording paper of the present invention (1) that dry film thickness is the ink-receiver layer of 32 μ m.

The composition of＜coating liquid B 〉

(1) boric acid (crosslinking agent) is 0.65 part

(2) zirconium carbonate ammonium is 6.5 parts

(" the ジ Le コ ゾ-Le AC-7 " that first rare element chemistry industry (strain) is made, 28% aqueous solution)

(3) ammonium carbonate is 6.0 parts

(4) ion exchange water is 83.8 parts

(5) surfactant is 0.2 part

(メ ガ Off ア Star Network F-1405, big Japanese ink chemistry (strain) is made)

Embodiment 2～6

Except the polymer 1 of being modulated ink-receiver layer coating liquid A being used among the embodiment 1 becomes polymer 2～6 respectively, fully similarly make ink-jet recording paper of the present invention (2)～(6) with embodiment 1.

Embodiment 7

Except in embodiment 1, in ink-receiver layer coating liquid A, adding 0.6 part of aluminium polychloride (40% aqueous solution, basic structure formula: Al again ₂(OH) ₅Cl) in addition, fully similarly make ink-jet recording paper of the present invention (7) with embodiment 1.

Embodiment 8～15

Except the polymer 1 of being modulated ink-receiver layer coating liquid A being used among the embodiment 7 becomes polymer 2～9 respectively, fully similarly make ink-jet recording paper of the present invention (8)～(15) with embodiment 1.

Embodiment 16

Except the coating liquid B among the embodiment 1 being become the coating liquid C of following composition, fully similarly make ink-jet recording paper of the present invention (16) with embodiment 1.

The composition of＜coating liquid C 〉

(1) boric acid (crosslinking agent) is 0.65 part

(2) polyallylamine " PAA-10C " 10% aqueous solution is 25 parts

(mordant, day east is spun (strain) and made)

(3) ion exchange water is 59.7 parts

(4) ammonium chloride (surface p H conditioning agent) is 0.8 part

(5) polyoxyethylene lauryl ether (surfactant) is 10 parts

(" the エ マ Le ゲ Application 109P " that flower king (strain) makes, 2% aqueous solution, HLB value 13.6)

(6) メ ガ Off ア Star Network " F1405 " 10% aqueous solution is 2.0 parts

(the fluorine class surfactant that big Japanese ink chemical industry (strain) is made)

Comparative example 1～3

Except the polymer 1 that is used for ink-receiver layer coating liquid A among the embodiment 1 being become following compd A～C respectively, fully similarly make the relatively ink-jet recording paper of usefulness (17)～(19) with embodiment 1.

Compound (A)

(S equivalent 11.0meq/g, I/O value 1.75)

Compound (B)

(S equivalent 1.94meq/g, I/O value 0.258)

Compound (C)

(S equivalent 0meq/g, I/O value 3.76)

Comparative example 4

Except the mixture that the polymer 1 that is used for ink-receiver layer coating liquid A among the embodiment 1 become above-claimed cpd A and C (A: C=1: 1, mass ratio) in addition, is fully similarly made the relatively ink-jet recording paper of usefulness (20) with embodiment 1.

Comparative example 5

Except the polymer 1 that is used for ink-receiver layer coating liquid A among the embodiment 1 being become poly-(2-methylacryoyloxyethyl trimethyl ammonium chloride), fully similarly make the relatively ink-jet recording paper of usefulness (21) with embodiment 1.

Comparative example 6

Except the polymer 1 that is used for ink-receiver layer coating liquid A among the embodiment 1 being become polybutadiene latex, fully similarly make the relatively ink-jet recording paper of usefulness (22) with embodiment 1.

Comparative example 7～10

Except the polymer 1 that is used for ink-receiver layer coating liquid A among the embodiment 7 being become above-claimed cpd A～C and following Compound D respectively, fully similarly make the relatively ink-jet recording paper of usefulness (23)～(26) with embodiment 7.

Compound (D)

(S equivalent 13.0meq/g, I/O value 2.33)

Comparative example 11

Except the polymer 1 that is used for ink-receiver layer coating liquid A among the embodiment 7 being become poly-(2-methylacryoyloxyethyl trimethyl ammonium chloride), fully similarly make the relatively ink-jet recording paper of usefulness (27) with embodiment 7.

Comparative example 12

Except the polymer 1 that will be used for ink-receiver layer coating liquid A among the embodiment 7 becomes polybutadiene latex, fully similarly make the relatively ink-jet recording paper of usefulness (28) with embodiment 7.

Comparative example 13 and 14

Except the polymer 1 that will be used for ink-receiver layer coating liquid A among the embodiment 7 becomes above-mentioned polymer 10 and 11 respectively, fully similarly make the relatively ink-jet recording paper of usefulness (29) and (30) with embodiment 7.

Comparative example 15

Except the polymer 1 that will be used for ink-receiver layer coating liquid A among the embodiment 7 becomes deionized water, fully similarly make the relatively ink-jet recording paper of usefulness (31) with embodiment 7.

(evaluation test)

For by above-mentioned each ink-jet recording paper of the present invention who obtains (1)～(16) and the ink-jet recording paper of usefulness (17)～(31) relatively, carry out following evaluation test.Result of the test is as shown in following table 1.

(glossiness)

Use digital angle Grossmeters (UGV-50DP, ス ガ testing machine (strain) is made) to measure 60 ° of glossiness in the ink-receiver layer surface of preceding each ink-jet recording paper of sensitization.

Glossiness is evaluated as A in time more than 45 °, below 55 °, is evaluated as B more than 35 °, during 45 ° of less thaies, is evaluated as C during 35 ° of less thaies.

(separating out test)

Various ink-jet recording papers were taken care of 10 days under 5 ℃ environment.The amount of separating out on ink-jet recording paper surface then detects by an unaided eye.

The average evaluation of not observing precipitate is A, and can confirm to have average evaluation out of question in a little precipitate and the practical application is B, can confirm that the average evaluation that a lot of precipitates is arranged and do not have practicality is C.

(ink absorption)

Use ink-jet printer (" PM-950C " that Seiko Epson (strain) is made), the image on the spot of sensitization Y (Huang), M (magenta), C (green grass or young crops), K (deceiving), B (indigo plant), G (green) and R (red) on by the above-mentioned ink jet recording paper that obtains, (after about 10 seconds) contact the paper extruding on this image at once then, the transfer printing of printing ink on this paper that detect by an unaided eye, and estimate according to following benchmark.If can not confirm the transfer printing of printing ink on paper, represent that then absorption of inks speed is good.

The average evaluation of not confirming printing ink transfer printing on paper fully is A, and the average evaluation of transfer printing that can the confirmation unit sub ink is B, can confirm that the transfer printing of printing ink of a great deal of and the average evaluation that does not have a practicality are C.

(through the time ooze profit)

Use ink-jet printer (" PM-950C " that Seiko Epson (strain) is made), the cancellate linear pattern (live width 0.28nm) of sensitization finished products-red printing ink and black ink adjacency on various ink-jet recording papers is measured vision concentration (ODfresh) by X lamp 310TR (manufacturing of X lamp company).After the mensuration the various ink-jet recording papers of sensitization are put into single page and press from both sides (clear file), at 35 ℃, relative humidity is keeping after 3 days in 80% the constant temperature and humidity cabinet, measure vision concentration (ODthermo) once more, calculate its change rate of concentration ((OD thermo-OD fresh)/OD fresh * 100).This change rate of concentration less than 20% be evaluated as A, more than 20%, less than 40% be evaluated as B, be evaluated as C more than 40%.Change rate of concentration is more little then show through the time moistening few more (well).

＜light resistance 〉

Use ink-jet printer (" PM-950C " that Seiko Epson (strain) is made), behind the image on the spot of sensitization finished products-red and cyan on the various ink-jet recording papers, by cutting off the ultraviolet filter of the following wavelength region may of 365nm, use Xenon Weather-ometer Ci65A (manufacturing of ATLAS company), under the environmental condition of 25 ℃ of temperature, relative humidity 32%, lit a lamp 3.8 hours, turn off then under the state of lamp and under the environmental condition of 20 ℃ of temperature, relative humidity 91%, placed 1 hour, with carrying out such circulation in 168 hours.Use reflection density to measure the image color of all kinds that meter (" Xrite938 " that Xrite company makes) is measured these test front and back, the survival rate of calculating each color density.

The survival rate of magenta density then is evaluated as A in the situation more than 90%, and the situation of 80%～less than 90% then is evaluated as B, and the situation of 70%～less than 80% then is evaluated as C, and the situation of less than 70% then is evaluated as D.

＜ozone resistance 〉

Use ink-jet printer (" PM-950C " that Seiko Epson (strain) is made), sensitization becomes the image on the spot of cyan respectively on various ink-jet recording papers, is keeping 24 hours under the environment of 2.5ppm at ozone concentration.Use reflection density to measure meter (" Xrite938 " that Xrite company makes) and measure before the keeping and magenta and cyan density after the keeping, the survival rate of calculating this cyan density.

Survival rate then is evaluated as A in the situation more than 85%, and more than 75%, the situation of less than 85% then is evaluated as B, more than 65%, the situation of less than 75% then is evaluated as C, the situation of less than 65% then is evaluated as D.

[table 1]

	Record-paper No.	Glossiness	Separate out test	Ink absorption	Through the time ooze profit	Light resistance	Ozone resistance
									Pinkish red	Blue or green
							Embodiment 1	?1			?A	?A	?A	?B	?A	?A	?B
Embodiment 2	?2	?A	?A	?A	?B	?B			?A	?B
							Embodiment 3	?3			?A	?A	?A	?A	?A	?A	?B
Embodiment 4	?4	?A	?A	?A	?A	?A			?A	?B
							Embodiment 5	?5			?A	?A	?A	?B	?A	?B	?B
Embodiment 6	?6	?A	?A	?A	?A	?A			?A	?B
							Embodiment 7	?7			?A	?A	?A	?A	?A	?A	?B
Embodiment 8	?8	?A	?A	?A	?A	?A			?A	?B
							Embodiment 9	?9			?A	?A	?A	?A	?A	?A	?A
Embodiment 10	?10	?A	?A	?A	?A	?A			?A	?A
							Embodiment 11	?11			?A	?A	?A	?A	?A	?A	?B
Embodiment 12	?12	?A	?A	?A	?A	?A			?A	?A
							Embodiment 13	?13			?A	?A	?A	?A	?A	?A	?B
Embodiment 14	?14	?A	?A	?A	?B	?A			?A	?B
							Embodiment 15	?15			?A	?A	?A	?B	?A	?A	?B
Embodiment 16	?16	?A	?A	?A	?A	?A			?A	?A
							Comparative example 1	?17			?A	?C	?A	?C	?B	?B	?B
Comparative example 2	?18	?C	?B	?A	?B	?C			?B	?C
							Comparative example 3	?19			?A	?A	?A	?B	?B	?C	?C
Comparative example 4	?20	?A	?A	?A	?B	?B			?B	?B
							Comparative example 5	?21			?A	?A	?A	?C	?B	?C	?C
Comparative example 6	?22	?B	?A	?A	?B	?C			?C	?C
							Comparative example 7	?23			?A	?C	?A	?C	?A	?B	?B
Comparative example 8	?24	?C	?B	?A	?B	?C			?B	?B
							Comparative example 9	?25			?C	?B	?A	?B	?B	?C	?B
Comparative example 10	?26	?A	?C	?A	?C	?B			?C	?C
							Comparative example 11	?27			?A	?A	?A	?B	?B	?C	?B
Comparative example 12	?28	?B	?A	?A	?B	?C			?C	?C
							Comparative example 13	?29			?A	?A	?A	?C	?B	?B	?C
Comparative example 14	?30	?A	?A	?A	?B	?C			?C	?C
							Comparative example 15	?31			?A	?A	?A	?B	?D	?D	?C

Result by table 1 can distinguish, recording medium of the present invention (ink-jet recording paper, embodiment 1～16) though for can suppress through the time ooze profit, again have under the ozone with high concentration environment for a long time certainly after the recording medium that the concentration survival rate is also high and ozone resistance is good of formed image.In addition, simultaneously also be that the concentration survival rate of formed image after the cyclic test that xenon lamp irradiation and high humidity are placed is also high, the light resistance good recording medium of light resistance of pinkish red color development particularly.

In addition, recording medium of the present invention is good in glossiness, absorption of inks speed, image section concentration, resistance to water.

On the other hand, that does not use polymer of the present invention relatively uses recording medium, fail to satisfy simultaneously ozone resistance and light resistance and through the time ooze lubricant nature.

Claims (14)

1. recording medium, on supporter, have in the recording medium of recording layer, it is characterized in that, contain in the described recording layer have thioether bond, the sulphur equivalent in inorganic nature/organic property of representing more than the 1.2meq/g and with organic conceptional diagram than (I/O) value at the polymer more than 0.5.

2. the recording medium described in claim 1 is characterized in that described polymer is the polymer that contains the part-structure shown in the following general formula (1),

General formula (1)

P-Y-S-

In the general formula (1), P represents to contain the polymer residue or the oligomer residue of repetitive, and Y represents the linking group of singly-bound or divalent.

3. the recording medium described in claim 1 or 2 is characterized in that described polymer is the polymer that contains the part-structure shown in the following general formula (2),

General formula (2)

In the general formula (2), R ¹Expression hydrogen atom or methyl, R ²Expression alkyl or aryl, J represents the linking group of singly-bound or divalent.

4. as any one the described recording medium in the claim 1～3, it is characterized in that described polymer is the polymer that contains the part-structure shown in the following general formula (3),

General formula (3)

In the general formula (3), R ¹¹And R ¹²Represent hydrogen atom or methyl independently of one another, R ¹³Expression alkyl or aryl, R ¹⁴, R ¹⁵And R ¹⁶Represent hydrogen atom or alkyl independently of one another, Y ¹Represent the linking group of divalent, m independently of one another with Z ¹And n ¹The mole % of repetitive in the expression polymer, 10≤m ¹≤ 95,5≤n ¹≤ 90, X ^-The expression balance anion.

5. as any one the described recording medium in the claim 1～4, it is characterized in that described polymer is the polymer that contains the part-structure shown in the following general formula (4),

General formula (4)

In the general formula (4), R ²⁰Expression hydrogen atom or methyl, R ²¹Expression alkyl or aryl, W represents the linking group of divalent, A represents to contain the unit of ethene unsaturated double-bond group, m ²And n ²The mole % of repetitive in the expression polymer, 50≤m ²≤ 95,5≤n ²≤ 50.

6. as any one the described recording medium in the claim 1～5, the sulphur equivalent that it is characterized in that described polymer is more than 3meq/g.

7. as any one the described recording medium in the claim 1～6, it is characterized in that described polymer is to have polymer water-soluble or the self-emulsifying characteristic.

8. as any one the described recording medium in the claim 1～7, it is characterized in that the polymer of described polymer for deriving by polybutadiene base polymer or polyisoprene base polymer.

9. as any one the described recording medium in the claim 1～8, it is characterized in that described recording layer is an ink-receiver layer, is ink jet recording medium.

10. the recording medium described in claim 9 is characterized in that also containing in the described ink-receiver layer water-soluble resin.

11. the recording medium described in claim 9 or 10 is characterized in that also containing in the described ink-receiver layer particulate.

12. as any one the described recording medium in the claim 9～11, it is characterized in that containing in the described ink-receiver layer can the cross-linked, water-soluble resin crosslinking agent.

13., it is characterized in that also containing in the described ink-receiver layer mordant as any one the described recording medium in the claim 9～12.

14. as any one the described recording medium in the claim 9～13, it is characterized in that described ink-receiver layer is to apply to contain described polymer, the coat that the coating liquid of particulate and water-soluble resin forms is through the formed layer of crosslinking curing, described crosslinking curing can be finished by the following method: to described coating liquid or/and add crosslinking agent in the following alkaline solution, and apply described coating liquid and when forming coat in (1), perhaps (2) apply in the dry way of the formed coat of described coating liquid and whenever this coat shows before falling rate of drying, pH are surpassed 7 alkaline solution and are provided on the described coat.